Skin compositions and methods of use thereof

ABSTRACT

The present invention provides durable, natural looking, non-invasive compositions that exhibit desired aesthetic qualities. Specifically, the compositions can be used for therapeutic treatments, including treatments of wounds and headaches. The invention pertains, at least in part, to therapeutic formulations for application to the skin that comprise a) a reactive reinforcing component; and b) a cross-linking component; in which the cross-linking component facilitates in situ formation of a film over the skin.

RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.13/430,586, filed Mar. 26, 2012, which is a Continuation ofInternational Application PCT/US2011/050016, filed Aug. 31, 2011, whichclaims the benefit of U.S. Provisional Patent Application No.61/500,455, filed Jun. 23, 2011; U.S. Provisional Patent Application No.61/499,002, filed Jun. 20, 2011; U.S. Provisional Patent Application61/496,420, filed Jun. 13, 2011; U.S. Provisional Patent Application No.61/493,020, filed Jun. 3, 2011; U.S. Provisional Patent Application No.61/489,119, filed May 23, 2011; U.S. Provisional Patent Application No.61/486,643, filed May 16, 2011; U.S. Provisional Patent Application No.61/472,995, filed Apr. 7, 2011; U.S. Provisional Patent Application No.61/446,377, filed Feb. 24, 2011; U.S. Provisional Patent Application No.61/432,458, filed Jan. 13, 2011; U.S. Provisional Patent Application No.61/412,531, filed on Nov. 11, 2010 and U.S. Provisional PatentApplication No. 61/378,504, filed on Aug. 31, 2010. The entire contentsof the foregoing applications are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

The skin acts an a protective barrier from the external environment.When damaged, a cascade of events is triggered to repair to the damagedtissue. Wound healing is a complex process, progressing through fourstages (inflammation, proliferation, remodeling, and epithelialization)to repair the damaged area. Although wound healing is a natural process,disruption of the events involved may lead to incomplete healing andfurther damage to the tissue. Current methods of treating wounds includeapplying a dressing to the wound to stem bleeding, prevent infection andencourage healing. Wound dressings are often made from breathablematerial (for example, gauze). Occlusive dressings have been used onwounds, but the effects of occlusion on wounded skin are not completelyunderstood (see e.g., Leow and Mailbach; J Dermatol Treat, (1997) 8,139-142).

However, current methods of using occlusion on wounded skin isunsatisfactory because current occlusive dressings are not durable,convenient, or long lasting. Moreover, some current occlusive coveringsrequire subjects to wrap plastic around the area to be treated, loweringsubject compliance because the treatment is cumbersome anduncomfortable. Lastly, current occlusive coverings do not permit theexposure of the wound to the environment to be modulated based upon thenature of the wound. For example, current occlusive dressings aredesigned to exclude both air and water, and generally it is not possibleto permit exposure to one and not the other.

Headaches cause pain in the head and neck and arise from a myriad ofcauses. While most are not life-threatening, headaches can be verypainful and debilitating. Headache remedies include from over thecounter analgesics, prescription medications, acupuncture and massage.

The commercially available polymer materials used in therapeuticproducts today do not necessarily provide the elasticity, environmentalresistance and skin adhesion for long lasting product performance nor dothey provide the aesthetic feel and appearance required by the consumerof therapeutic products.

SUMMARY OF THE INVENTION

The present invention provides durable, natural looking, non-invasivecompositions that exhibit desired aesthetic qualities for therapeutictreatments. Specifically, the compositions can be used for the treatmentof wounds and headaches. In addition, the compositions of the inventioncan be used to deliver agents to the subject in need thereof.

In one embodiment, the invention pertains, at least in part, to methodsfor treating wounds, comprising applying to a subject's skin aformulation comprising a) a first reactive reinforcing component; and b)a second cross-linking component; in which the cross-linking componentcatalyzes an in situ cross-linking of the reactive reinforcingcomponent, such that a film is formed on the wound, thereby treating thewound.

In one embodiment, the invention pertains, at least in part, to methodsfor preventing a wound from occurring, comprising applying to a wound ona subject a formulation comprising a) a first reactive reinforcingcomponent; and b) a second cross-linking component; in which thecross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component, such that a film is formed on the wound,thereby preventing the occurrence of the wound.

The current invention has many advantages. The invention provides adurable, convenient, long-lasting occlusive coating. The formulation,composition or film of the invention provides a transparent or a tintedcoating for the treatment site. The formulation, composition or film ofthe invention is more comfortable because it forms a layer over the skinand therefore increases subject compliance as compared to currentocclusive coatings. Moreover, the chemical and physical properties ofthe formulation, composition or film of the invention are tunable toform an occlusive coating that is best suited for the location on thesubject and the type of wound to be treated.

In one embodiment, the invention pertains, at least in part, to methodsfor delivering an agent to a subject, comprising applying to thesubject's skin a formulation comprising a) a first reactive reinforcingcomponent optionally comprising one or more agents; and b) a secondcross-linking component optionally comprising one or more agents; inwhich the cross-linking component catalyzes an in situ cross-linking ofthe reactive reinforcing component such that a film is formed on theskin, thereby delivering the agent to the subject.

In one embodiment, the invention pertains, at least in part, to methodsof treating a headache in a subject comprising applying to anappropriate area of the subject's skin a formulation in an amounteffective to lift the subject's brow, the formulation comprising a) afirst reactive reinforcing component and b) a second cross-linkingcomponent; in which the cross-linking component catalyzes an in situcross-linking of the reactive reinforcing component such that a film isformed on the skin, thereby treating the headache. In one embodiment,the invention pertains, at least in part, to therapeutic formulationsfor application to a subject's body, comprising at least one preselectedfunction modulating component, in which the composition forms atherapeutic film upon application to the subject's body.

In one embodiment, the invention pertains, at least in part, totherapeutic formulations for application to a subject's skin that targeta treatment area on a subject's body, comprising at least onepreselected treatment specific component, wherein the composition formsa therapeutic film upon application to the target treatment area on thesubject's body.

In one embodiment, the invention pertains, at least in part, to a filmremoving cleanser for use in removing a therapeutic film, wherein thefilm is prepared by a process comprising the steps of applying areactive reinforcing component to skin; and applying a cross-linkingcomponent to said reactive reinforcing component, and wherein saidcross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component.

In another embodiment, the invention pertains, at least in part, to afilm removing cleanser comprising a film wetting component, apenetration component, a film swelling component and a film releasecomponent.

In some embodiments, the invention pertains to a formulation forrepairing a therapeutic film applied to skin, wherein said formulationcomprises a) a first reactive reinforcing component and b) a secondcross-linking component, wherein the cross-linking component catalyzesan in situ cross-linking of the reactive reinforcing component such thata film is formed on the skin.

In some embodiments, the invention pertains, at least in part, to amethod for repairing a therapeutic; film applied to skin comprising thesteps of a) identifying an area of the film in need of repair; b)optionally smoothing the edges of the film; and c) applying aformulation for repairing the film, wherein the formulation comprises afirst reactive reinforcing component and a second cross-linkingcomponent, wherein the cross-linking component catalyzes an in situcross-linking of the reactive reinforcing component such that a film isformed on the skin, thereby repairing the therapeutic film.

In some embodiments, the invention pertains, at least in part, to a kitfor repairing a therapeutic film, the kit comprising a formulationcomprising a) a first reactive reinforcing component and b) a secondcross-linking component, wherein the cross-linking component catalyzesan in situ cross-linking of the reactive reinforcing component such thata film is formed on the skin.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart illustrating the change in the Young's Modulus of theskin after the application of a formulation of the invention. The changein Young's Modulus indicates that there is a reduction in the stiffnessof skin upon application of the formulation.

FIG. 2 is a chart illustrating the change in the retraction time afterapplication of a formulation of the invention. The change in theretraction time indicates that the skin is more elastic upon applicationof the formulation.

DETAILED DESCRIPTION OF THE INVENTION

In some embodiments, the invention pertains, at least in part, totherapeutic formulations for application to the skin that comprise a) areactive reinforcing component; and b) a cross-linking component; inwhich the cross-linking component catalyzes an in situ cross-linking ofthe reactive reinforcing component, such that a therapeutic film isformed on the skin.

The language “therapeutic formulation” or “formulation” includestherapeutic compositions that, when applied to the body of a subject inneed of treatment, form a film on the body resulting in a therapeuticbenefit to the subject. Therapeutic benefits include, but are notlimited to, wound healing and amelioration of headache pain.

The language “wounds” includes injuries to the skin wherein the skin istorn, cut or punctured. A wound is a break in the skin. In oneembodiment, the wound is caused by skin contact with a foreign object.The break in the skin may cause external bleeding. Wounds include openwounds, for example, abrasions, lacerations, incisions, punctures,avulsions, or amputations. Wounds also include burn wounds. A burn is atype of injury to flesh caused by heat, electricity, chemicals, light,radiation or friction.

In one embodiment of the invention, the compositions, formulations orfilms of the invention treat the wound of the subject, in addition tomasking, concealing, or covering the wound.

In at least one embodiment, a wound does not include skin or bodyimperfection or a dermatological disorders.

The language “skin or body imperfections” include those items on asubject's skin that the subject perceives as a blemish or a flaw.Examples of skin imperfections include port wine stain or nevus flammeus(e.g., nevus flammeus nuchae or midline nevus flammeus) melasma,wrinkles, blemishes, acne, moles, scars, tattoos, bruises, skindisfigurements, birth marks, sun damage, age damage, uneven skin tone,sagging skin, skin roughness, hyperpigmentation, enlarged pores,telangiectasia, redness, shine, cellulite, stretch marks or loss of skinelasticity.

The language “dermatological disorder” includes disorders that cause atleast one symptom on the skin of a subject requiring medical treatment.In one embodiment, dermatological disorders are caused by autoimmunedisorders. In another embodiment, a dermatological disorder is caused byenvironmental factors, such a allergens or chemicals. Examples ofsymptoms of dermatological disorders requiring treatment is dermatitis,itchy skin, dry skin, crusting, blistering, or cracking skin, skinedema, or skin lesion formation. Dermatological disorders include, butare not limited to, lichen simplex chronicus, cutaneous lupus (e.g.,acute cutaneous lupus, subacute cutaneous lupus, chronic cutaneouslupus, chilblain lupus erythematosus, discoid lupus erythematosus, lupuserythematosus-lichen planus overlap syndrome, lupus erythematosuspanniculitis, tumid lupus erythematosus and verrucous lupuserythematosus), psoriasis (e.g., psoriasis vulgaris, psoriaticerythroderma, pustular psoriasis, drug-induced psoriasis, inversepsoriasis, seborrheic-like psoriasis and guttate psoriasis), eczema(e.g., atopic, eczema, atopic dermatitis, contact dermatitis, xeroticeczema, seborrhoeic dermatitis, dyshidrosis, discoid eczema, venouseczema, dermatitis herpetiformis, neurodermatitis andautoeczematization), or chronic dry skin.

In one embodiment, the therapeutic formulations include a reactivereinforcing component and a cross-linking component. The language“reactive reinforcing component” includes a component that, when appliedto the skin as a first component, is the basis of the therapeutic filmthat is formed upon application of the cross-linking component to thereactive reinforcing component. In one embodiment, the reactivereinforcing component includes at least one reactive constituent and atleast one reinforcing constituent.

The language “reactive constituent” includes one or more constituents ofthe reactive reinforcing component that provide the reactivefilm-forming elements of the formulation. In some embodiments, thereactive constituent includes at least one polysiloxane, polyethyleneoxide, polypropylene oxide, polyurea, polyurethane, polyester (includingpolylactic-co-glycolic acid, polycaprolactone, polylactic acid,polyglycolic acid, and polyhydroxybutyrate, polyamide, or polysulfone.In another embodiment, the reactive constituent is a compound of formulaI:

wherein

W is R¹R²R³SiO—, —OR⁴, —NR⁵R⁶, —CR⁷R⁸R⁹ or C₅₋₁₀ aryl;

X is —R¹¹R¹²Si—O—, —OCONR¹³—, —NR¹⁴CONR¹⁵—, —CO—, —NR¹⁶CO—, —SO₂—, —O—,—S— or —NR¹⁷—;

V is absent, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, —O—, —NR¹⁰— or —S—;

Y is —R¹⁸R¹⁹Si—O—, —OCONR²⁰—, —NR²¹CONR²²—, —CO—, —NR²³CO—, —SO₂—, —O—,—S— or —NR²⁴;

Z is —SiR²⁵R²⁶R²⁷, —OR²⁸, —NR²⁹R³⁰, —CR³¹R³²R³³ or C₅₋₁₀ aryl; R¹, R²,R³, R⁷, R⁸, R⁹, R¹¹, R¹², R¹⁸R¹⁹, R²⁵, R²⁶, R²⁷, R³¹, R³² and R³³ areeach independently hydrogen, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl,hydroxyl or C₁₋₂₀ alkoxyl;

R⁴, R⁵, R⁶, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R²⁰, R²¹, R²², R²³, R²⁴, R²⁸, R²⁹and R³⁰ are each independently hydrogen, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl,C₅₋₁₀ aryl; and

s and t are each independently an integer from about 0 to about 6000.

X and Y of formula I represent an independent “monomer unit.” The numberof X and Y monomer units present in formula I is provided by the valueof s and t, respectively. Representative monomer units include:

where R is as for defined for R¹, R², R³, etc, above.It is understood that when more than one X (or Y) monomer unit ispresent (e.g. s (or t) is more than one), the values for R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸R¹⁹, R²⁰, R²¹, R²², R²³, and R²⁴ are selectedindependently for each individual monomer unit described by —[X]_(s)—(or —[Y]_(t)—). For example, if the value of the monomer unit X is—R¹¹R¹²Si—O— and the value of s is 3, then —[X]_(s)— is:—[R¹¹R¹²Si—O—R¹¹R¹²Si—O—R¹¹R¹²Si—O]—.In this example, it is understood that the three R¹¹ groups present inmay be the same or different from each other, for example, one R¹¹ maybe hydrogen, and the two other R¹¹ groups may be methyl.

W and Z of formula I represent independent terminal caps, one on eachend of the. For example, terminal caps include:

wherein

denotes attachment to a monomer unit and wherein R is as for defined forR¹, R², R³, etc, above. In one embodiment,

W is R¹R²R³SiO—, —OR⁴, —NR⁵R⁶, —CR⁷R⁸R⁹ or C₅₋₁₀ aryl;

X is —R¹¹R¹²Si—O—, or —NR¹⁴CONR¹⁵—;

V is absent, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, —O—, —NR¹⁰— or —S—;

Y is —R¹⁸R¹⁹Si—O—, or —NR²¹CONR²²—;

Z is —SiR²⁵R²⁶R²⁷, —OR²⁸, —NR²⁹R³⁰, —CR³¹R³²R²³ or C₅₋₁₀ aryl;

-   -   R¹, R², R³, R⁷, R⁸, R⁹, R¹¹, R¹², R¹⁸R¹⁹, R²⁵, R²⁶, R²⁷, R³¹,        R³² and R³³ are each independently hydrogen, C₁₋₂₀ alkyl, C₂₋₂₀        alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxyl;

R⁴, R⁵, R⁶, R¹⁴, R¹⁵, R²¹, R²², R²⁸, R²⁹ and R³⁰ are each independentlyhydrogen, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl; and

s and t are each independently an integer from about 0 to about 6000,wherein the sum of s and t is not 0.

In one embodiment,

W is R¹R²R³SiO—, —CR⁷R⁸R⁹ or C₅₋₁₀ aryl;

X is —R¹¹R¹²Si—O—, or —NR¹⁴CONR¹⁵—;

V is absent, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, or C₅₋₁₀ aryl;

Y is —R¹⁸R¹⁹Si—O—, or —NR²¹CONR²²—;

Z is —SiR²⁵R²⁶R²⁷, —CR³¹R³²R³³ or C₅₋₁₀ aryl;

R¹, R², R³, R⁷, R⁸, R⁹, R¹¹, R¹², R¹⁸R¹⁹, R²⁵, R²⁶, R²⁷, R³¹, R³² andR³³ are each independently hydrogen, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀aryl, hydroxyl or C₁₋₂₀ alkoxyl;

R¹⁴, R¹⁵, R²¹, and R²² are each independently hydrogen, C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₅₋₁₀ aryl; and

s and t are each independently an integer from about 0 to about 6000,wherein the sum of s and t is not 0.

In one embodiment, V is absent, W is R¹R²R³SiO—; X is —R¹¹R¹²Si—O—; Y is—R¹⁸R¹⁹Si—O—; Z is —SiR²⁵R²⁶R²⁷; and R¹, R², R³, R¹¹, R¹², R¹⁸, R¹⁹,R²⁵, R²⁶ and R²⁷ are each independently selected from C₁₋₂₀ alkyl (e.g.,C₁ alkyl, such as methyl) or C₂₋₂₀ alkenyl (e.g., C₂ alkenyl, such asvinyl). In one embodiment, at least one of R¹, R², R³, R¹¹, R¹², R¹⁸,R¹⁹, R²⁵, R²⁶ and R²⁷ is C₂₋₂₀ alkenyl, for example, C₂ alkenyl (e.g.,vinyl). In another embodiment, at least two of R¹, R², R³, R¹¹, R¹²,R¹⁸, R¹⁹, R²⁵, and R²⁷ are C₂₋₂₀ alkenyl, for example, C₂ alkenyl (e.g.,vinyl). In some embodiments, at least one of R¹, R², R³, R²⁵, R²⁶ andR²⁷ are each C₂₋₂₀ alkenyl, for example, C₂ alkenyl (e.g., vinyl).

In one embodiment, V is absent, W is R¹R²R³SiO—; X is —R¹¹R¹²Si—O—; Y is—R¹⁸R¹⁹Si—O—; Z is —SiR²⁵R²⁶R²⁷; and R¹, R², R³, R²⁵, R²⁶ and R²⁷ areeach independently selected from C₁₋₂₀ alkyl (e.g., C₁ alkyl, such asmethyl) or C₂₋₂₀ alkenyl (e.g., C₂ alkenyl, such as vinyl); and R¹¹,R¹², R¹⁸, and R¹⁹ are each independently selected from C₁₋₂₀ alkyl(e.g., C₁ alkyl, such as methyl). In one embodiment, at least one of R¹,R², R³, and at least one of R²⁵, R²⁶ and R²⁷ is C₂₋₂₀ alkenyl, forexample, C₂ alkenyl (e.g., vinyl). In one embodiment, one of R¹, R², R³is C₂ alkenyl (e.g., vinyl) and the others are C₁₋₂₀ alkyl (e.g., C₁alkyl, such as methyl), and at least one of R²⁵, R²⁶ and R²⁷ is C₂₋₂₀alkenyl, for example, C₂ alkenyl (e.g., vinyl) and the others are C₁₋₂₀alkyl (e.g., C₁ alkyl, such as methyl). In one embodiment, at least oneof R¹¹ or R¹² and at least one of R¹⁸ or R¹⁹ is C₂₋₂₀ alkenyl, forexample, C₂ alkenyl (e.g., vinyl) for at least one monomer unit. In oneembodiment, one of R¹¹ or R¹² is C₂ alkenyl (e.g., vinyl) and the othersare C₁₋₂₀ alkyl (e.g., C₁ alkyl, such as methyl), and at least one ofR¹⁸ or R¹⁹ is C₂₋₂₀ alkenyl, for example, C₂ alkenyl (e.g., vinyl) andthe others are C₁₋₂₀ alkyl (e.g., C₁ alkyl, such as methyl) for at leastone monomer unit.

In some embodiments, the organopolysiloxane includes vinyl moieties onlyat the terminal caps of the polymer. In some embodiments, theorganopolysiloxane include vinyl moieties only in the monomer units, butnot at the terminal cap of the polymer. In other embodiments, theorganopolysiloxane includes vinyl moieties at both the terminal cap orin the monomer unit of the polymer. In one embodiment, the polymerincludes two vinyl moieties located either at the terminal cap, orwithin the monomer unit, or a combination thereof.

In one embodiment, on average at least two vinyl moieties are present inthe polymer. In a specific embodiment, at least two vinyl moieties arepresent in the polymer and at least two vinyl moieties are present onthe two terminal caps of the polymer. In a specific embodiment, only twovinyl moieties are present in the polymer. In a specific embodiment,only two vinyl moieties are present in the polymer and are located oneach of the terminal caps. In a specific embodiment, on average at leasttwo vinyl moieties are present in the polymer and at least two vinylmoieties are present in one or more monomer units of the polymer. In aspecific embodiment, at least two vinyl moieties are present anywhere inthe polymer, but separated from another vinyl moiety by about 2000monomer units, for example, 1500, 1600, 1700, 1800, 1900, 2000, 2100,2200, 2300, 2400, or 2500 monomer units. In a specific embodiment, onaverage at least two vinyl moieties are present anywhere in the polymer,but separated from another vinyl moiety by about 850 monomer units, forexample, 350, 450, 550, 650, 750, 850, 950, 1050, 1150, 1250, or 1350monomer units. In a specific embodiment, on average greater two vinylmoieties are present anywhere in the polymer, but separated from anothervinyl moiety by about 40 monomer units, for example, 5, 10, 15, 20, 25,30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 monomer units. In aspecific embodiment, one or more Si—H units are present in addition tothe vinyl moiety. Alternatively, in one embodiment, if a vinyl moiety ispresent then a Si—H is not present.

In one embodiment, V is absent, W is R¹R²R³SiO—; X is —R¹¹R¹²Si—O—; Y is—R¹⁸R¹⁹Si—O—; Z is —SiR²⁵R²⁶R²⁷; R¹R², R³, R¹¹, R¹², R¹⁸, R¹⁹, R²⁵R²⁶and R²⁷ are each independently are each independently selected fromhydrogen or C₁₋₂₀ alkyl (e.g., C₁ alkyl, such as methyl). In oneembodiment, R¹, R², R³, R²⁵, R²⁶ and R²⁷ are each independently selectedfrom C₁₋₂₀ alkyl (e.g., C₁ alkyl, such as methyl); and R¹¹, R¹², R¹⁸,and R¹⁹ are each independently selected from hydrogen or C₁₋₂₀ alkyl(e.g., C₁ alkyl, such as methyl), wherein at least one of and R¹¹, R¹²,R¹⁸, and R¹⁹ are hydrogen for at least one monomer unit. In oneembodiment, on average greater than two Si—H units (e.g. one or more ofR¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen) are present in the polymer, forexample 3-15 Si—H units may be present. In a specific embodiment, 8 Si—Hunits are present. In one embodiment, one or more Si—H units (e.g. oneor more of R¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen) are present in thepolymer. In one embodiment, at least two monomer units include a —Si—Hunit (e.g. one or more of R¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen). In oneembodiment, at least three monomer units include a—Si—H unit (e.g. oneor more of R¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen). In one embodiment, atleast four monomer units include a —Si—H unit (e.g. one or more of R¹¹,R¹², R¹⁸, and R¹⁹ is hydrogen). In one embodiment, at least five monomerunits include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, and R¹⁹is hydrogen). In one embodiment, at least six monomer units include a—Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen). Inone embodiment, at least seven monomer units include a —Si—H unit (e.g.one or more of R¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen). In one embodiment,at least eight monomer units include a —Si—H unit (e.g. one or more ofR¹¹, R¹², R¹⁸, and R¹⁹ is hydrogen). In one embodiment, a Si—H unit maybe present in one or both the terminal caps in addition to being presentin a monomer unit as described above. In a specific embodiment,Si-(alkyl) or Si-(vinyl) units may also be present in the polymer. In aspecific embodiment, only Si—CH₃ and Si—H units are present. In aspecific embodiment, monomer units or terminal caps include C₁-C₂₀alkyl,specifically methyl groups, for the non-Si—H positions of the polymer.

In a specific embodiment, on average at least two Si—H units are presentin the polymer. In a specific embodiment, on average at least two Si—Hmoieties are present anywhere in the polymer, but separated from anotherSi—H moiety by about 2000 monomer units, for example, 1500, 1600, 1700,1800, 1900, 2000, 2100, 2200, 2300, 2400, or 2500 monomer units. In aspecific embodiment, on average at least two Si—H units are presentanywhere in the polymer, but separated from another Si—H moiety by about850 monomer units, for example, 350, 450, 550, 650, 750, 800, 850, 950,1050, 1150, 1250, or 1350 monomer units. In a specific embodiment, onaverage greater than two Si—H units are present anywhere in the polymer,but separated from another Si—H moiety by about 40 monomer units, forexample, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or80 monomer units.

In one aspect of any one of the above embodiments, the sum of s and t isan integer from about 1000 to about 8000; from about 1300 to about 2700;from about 1500 to about 2700; from about 1600 to about 2600; from about1600 to about 2500; from about 1700 to about 2500; from about 1800 toabout 2400; from about 1800 to about 2300; from about 1900 to about2300; from about 2000 to about 2200; from about 2050 to about 2150; fromabout 2100.

In one aspect of any one of the above embodiments, the sum of s and t isan integer from about 200 to about 1100; from about 600 to about 1100;from about 700 to about 1000; from about 800 to about 900; from about825 to about 875; from about 850; from about 200 to about 800; fromabout 225 to about 700; from about 250 to about 600; from about 275 toabout 500; from about 300 to about 400; from about 350 to about 400;from about 375. In a specific embodiment, the sum of s and t is aninteger from about 850.

In one aspect of any one of the above embodiments, the sum of s and t isan integer from about 5 to about 1300; from about 10 to about 1100; fromabout 10 to about 600; from about 15 to about 500; from about 15 toabout 400; from about 20 to about 300; from about 20 to about 200; fromabout 25 to about 100; from about 25 to about 75; from about 30 to about50; from about 40.

In some embodiments, the reactive constituent comprises at least oneorganopolysiloxane. The term “organopolysiloxane” includes compounds offormula II:

wherein R^(1a), R^(2a), R^(3a), R^(4a), R^(5a), R^(6a), R^(7a), R^(8a),R^(9a) and R^(10a) are each independently selected from hydrogen, C₁₋₂₀alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxyl and p and qare each independently an integer from between 10 and about 6000.

In some embodiments, the organopolysiloxane is a compound of formulaIIa:

wherein R^(1a), ′ R^(3a′), R^(4a′), R^(5a′), R^(6a′), R^(8a′), R^(9a′)and R^(10a′) are each independently selected from hydrogen, C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxyl and p and q areeach independently an integer from between 10 and about 6000. In oneembodiment, R^(1a), ′ R^(3a′), R^(4a′), R^(5a′), R^(6a′), R^(8a′),R^(9a′) and R^(10a′) are alkyl (e.g., C₁ alkyl, such as methyl).

The term “alkyl” includes both branched and straight-chain saturatedaliphatic hydrocarbon groups having the specified number of carbonatoms. The term “C₁₋₂₀ alkyl” includes branched and straight chainaliphatic groups having between 1 and 20 carbons. Examples of alkylmoieties include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl,t-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl,isopentyl, and s-pentyl. Moreover, the term alkyl includes both“unsubstituted alkyls” and “substituted alkyls,” the latter of whichrefers to alkyl moieties having substituents (e.g., F, Cl, Br, I, NO₂,CN, alkyl, aryl, hydroxyl, alkoxy, COCH₃ and the like) replacing ahydrogen on one or more carbons of the hydrocarbon backbone.

The term “alkenyl” includes the specified number of hydrocarbon atoms ineither straight or branched configuration with one or more unsaturatedcarbon-carbon bonds that may occur in any stable point along the chain,such as ethenyl and propenyl. The language “C₂₋₂₀ alkenyl” includesbranched and straight chain hydrocarbon groups with between 1 and 20carbons and with one or more unsaturated carbon-carbon bonds. Moreover,the term “alkenyl” includes both “unsubstituted alkenyls” and“substituted alkenyls,” the latter of which refers to alkenyl moietieshaving substituents (e.g., F, Cl, Br, I, NO₂, CN, alkyl, aryl, hydroxyl,alkoxy, COCH₃ and the like) replacing a hydrogen on one or more carbonsof the hydrocarbon backbone.

The term “aryl” includes 5-10 membered monocyclic, bicyclic, ortricyclic rings, wherein at least one ring, if more than one is present,is aromatic. The term “aryl” also includes “heteroaryl” moieties inwhich one heteroatom (e.g., N, O or S) replaces one or more carbons inthe monocyclic, bicyclic, or tricyclic ring. The term “aryl” alsoincludes both “unsubstituted aryls” and “substituted aryls,” the latterof which refers to aryl moieties having substituents (e.g., F, Cl, Br,I, NO₂, CN, alkyl, hydroxyl, alkoxy, COCH₃ and the like) replacing ahydrogen on one or more carbons aromatic ring.

The term “hydroxyl” includes —OH.

The term “alkoxy” includes moieties in which an O is covalently bondedto a C₁₋₂₀ alkyl group, as defined above.

In some embodiments, the organopolysiloxane is vinyl terminated. Thelanguage “vinyl terminated organopolysiloxane” includesorganopolysiloxanes of formula II in which one or both of R^(2a) andR^(7a) are substituted with a C₂ alkyl moiety, for example, a vinylmoiety (e.g., —CH═CH₂). In a specific embodiment, a “vinyl terminatedorganopolysiloxane” includes organopolysiloxanes of formula II in whichone or both of R^(2a) and R^(7a) are substituted with a C₂ alkyl moiety,for example, a vinyl moiety (e.g., —CH═CH₂), and R^(1a), R^(3a), R^(4a),R^(5a), R^(6a), R^(8a), R^(9a) and R^(10a) are independently selectedfrom C₁₋₂₀ alkyl, for example, methyl.

In other embodiments, the organopolysiloxane is selected from: vinylterminated polydimethylsiloxane; vinyl terminateddiphenylsiloxane-dimethylsiloxane copolymers; vinyl terminatedpolyphenylmethylsiloxane, vinylphenylmethyl terminatedvinylphenylsiloxane-phenylmethylsiloxane copolymer; vinyl terminatedtrifluoropropylmethylsiloxane-dimethylsiloxane copolymer; vinylterminated diethylsiloxane-dimethylsiloxane copolymer;vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxyterminated; vinylmethylsiloxane-dimethylsiloxane copolymers, silanolterminated; vinylmethylsiloxane-dimethylsiloxane copolymers, vinylterminated; vinyl gums; vinylmethylsiloxane homopolymers; vinylT-structure polymers; monovinyl terminated polydimethylsiloxanes;vinylmethylsiloxane terpolymers; vinylmethoxysilane homopolymers andcombinations thereof.

In some embodiments, the organopolysiloxane is a high viscosityorganopolysiloxane, a low viscosity organopolysiloxane or a combinationthereof.

When the organopolysiloxane is a combination of high and low viscosityorganopolysiloxanes, the combination of a high viscosity and a lowviscosity vinyl organosiloxane provides a bimodal distribution oforganosiloxane molecular weights. In at least one embodiment, theorganopolysiloxane is a combination of high and low viscosityvinyl-terminal organopolysiloxanes providing a bimodal distribution ofthe vinyl-terminated organopolysiloxane. In one embodiment, theorganopolysiloxane is a combination of formulas I, II, IIa, IIb, andIIc, specifically, of formula IIa, IIb and/or IIc, or more specifically,of formula IIb and IIc, providing a bimodal distribution of thevinyl-terminated organopolysiloxane. In one embodiment, the bimodaldistribution of polymer molecular weight is represented by a ratio ofthe molecular weights (for example, the sum of s and t) of the highviscosity organopolysiloxanes to the low viscosity organopolysiloxane.In one embodiment, this ratio is from 2 to 3. In a specific embodiment,this ratio is 2.5.

The term “viscosity” refers to the measure of the resistance of a fluidwhich is being deformed by either shear stress or tensile stress. One ofskill in the art without undue experimentation would be able todetermine how to measure the viscosity of a fluid, for example, using aviscometer or a rheometer. Representative methods include use of acapillary viscometer, rotational viscometer or rheometer to measureviscosity at an instrument specific strain. Specific methods fordetermining the viscosity of a fluid are shown in Example 7.

The language “high viscosity organopolysiloxane” includesorganopolysiloxanes with a viscosity of between about 100,000 and about500,000 cSt or cP at 25° C., for example, between about 110,000 andabout 450,000 cSt or cP at 25° C. between about 120,000 and about400,000 cSt or cP at 25° C., between about 125,000 and about 350,000 cStor cP at 25° C., between about 130,000 and about 300,000 cSt or cP at25° C., between about 135,000 and about 250,000 cSt or cP at 25° C.,between about 140,000 and about 200,000 cSt or cP at 25° C., betweenabout 145,000 and about 190,000 cSt or cP at 25° C., between about150,000 and about 185,000 cSt or cP at 25° C., between about 155,000 andabout 175,000 cSt or cP at 25° C., or between about 160,000 and about170,000 cSt or cP at 25° C. In some embodiments, the viscosity of thehigh viscosity organopolysiloxane is between about 140,000 and about200,000 cSt or cP at 25° C. In one embodiment, the high viscosityorganopolysiloxane has a viscosity of about 165,000 cSt or cP at 25° C.

In one embodiment, the average molecular weight of the high viscosityorganopolysiloxane is between about 100,000 and about 200,000 Da, forexample, between about 115,000 and about 195,000 Da, between about120,000 and about 190,000 Da, between about 125,000 and about 185,000Da, between about 130,000 and about 180,000 Da, between about 135,000and about 175,000 Da, between about 140,000 and about 170,000 Da,between about 145,000 and about 165,000 Da or between about 150,000 andabout 160,000 Da. In one embodiment, the average molecular weight of thehigh viscosity organopolysiloxane is about 155,000 Da.

In some embodiments, the high viscosity organopolysiloxane is of formulaII, in which R^(2a) and R^(7a) are C₂₋₂₀ alkenyl, for example, C₂alkenyl (e.g., vinyl) and R^(1a), R^(3a), R^(4a), R^(5a), R^(6a),R^(8a), R^(9a) and R^(10a) are each C₁₋₂₀ alkyl, for example, C₁ alkyl(e.g., methyl). In some embodiments, the high viscosityorganopolysiloxane is vinyl terminated. In other embodiments, the highviscosity organopolysiloxane is vinyl terminated polydimethylsiloxane.

In some embodiments, the vinyl terminated high viscosityorganopolysiloxane has a weight percent of vinyl of between about 0.010and about 0.100, for example, between about 0.015 and about 0.080,between about 0.020 and about 0.075, between about 0.025 and about0.060, or between about 0.030 and about 0.050. In one embodiment, thehigh viscosity organopolysiloxane has a weight percent of vinyl ofbetween about 0.030 and about 0.040.

In other embodiments, the high viscosity organopolysiloxane has a vinylequivalent per kilogram of between about 0.0100 and about 0.0200, forexample, between about 0.0110 and about 0.0190, between about 0.0115 andabout 0.0180, between about 0.0120 and about 0.0170, between about0.0125 and about 0.0165 or between about 0.013 and about 0.016.

In one embodiment, the high viscosity organopolysiloxane has on averageat least two vinyl units per high viscosity organopolysiloxane. In oneembodiment, the monomer unit including a vinyl moiety are spacedthroughout the polymer. In one embodiment, the vinyl-containing monomerunit is spaced about 2000 monomer units away from anothervinyl-containing, monomer unit or a vinyl-containing terminal cap. Forexample, the vinyl units in the high viscosity organopolysiloxanes areseparated by 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400,or 2500 monomer units.

In some embodiments, the high viscosity organopolysiloxane is selectedfrom: vinyl terminated polydimethylsiloxane; vinyl terminateddiphenylsiloxane-dimethylsiloxane copolymers; vinyl terminatedpolyphenylmethylsiloxane, vinylphenylmethyl terminatedvinylphenylsiloxane-phenylmethylsiloxane copolymer; vinyl terminatedtrifluoropropylmethylsiloxane-dimethylsiloxane copolymer; vinylterminated diethylsiloxane-dimethylsiloxane copolymer;vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxyterminated; vinylmethylsiloxane-dimethylsiloxane copolymers, silanolterminated; vinylmethylsiloxane-dimethylsiloxane copolymers, vinylterminated; vinyl gums; vinylmethylsiloxane homopolymers; vinylT-structure polymers; monovinyl terminated polydimethylsiloxanes;vinylmethylsiloxane terpolymers; vinylmethoxysilane homopolymers andcombinations thereof.

The language “low viscosity organopolysiloxane” includesorganopolysiloxanes with a viscosity of between about 500 and about50,000 cSt or cP at 25° C., for example, between about 1,000 and about45,000 cSt or cP at 25° C., between about 1,500 and about 40,000 cSt orcP at 25° C., between about 2,000 and about 35,000 cSt or cP at 25° C.,between about 2,500 and about 30,000 cSt or cP at 25° C., between about3,000 and about 25,000 cSt or cP at 25° C., between about 3,500 andabout 20,000 cSt or cP at 25° C., between about 4,000 and about 15,000cSt or cP at 25° C., or between about 4,000 and about 12,000 cSt or cPat 25° C. In some embodiments, the low viscosity organopolysiloxaneincludes organopolysiloxanes with a viscosity of between about 100 andabout 5,000 cSt or cP at 25° C., for example, between about 200 andabout 4000 cSt cP at 25° C., between about 300 and about 3000 cSt or cPat 25° C., between about 400 and about 2000 cSt or cP at 25° C. orbetween about 750 and about 1500 cSt or cP at 25° C. In one embodiment,the low viscosity organopolysiloxane has a viscosity of about 10,000 cStor cP at 25° C. In some embodiments, the low viscosityorganopolysiloxane has a viscosity of about 1000 cSt or cP at 25° C.

In some embodiments, the low viscosity organopolysiloxane has an averagemolecular weight of between about 20,000 and about 80,000 Da, forexample, between about 50,000 and about 75,000 Da, between about 55,000and about 70,000 Da, between about 60,000 and about 65,000 Da or between62,000 and about 63,000 Da, in one embodiment, the low viscosityorganopolysiloxane has an average molecular weight of about 62,700 Da.In one embodiment, the low viscosity organopolysiloxane has an averagemolecular weight of about 28,000 Da.

In some embodiments, the low viscosity organopolysiloxane is of formulaII, in which R^(2a) and R^(7a) are C₂₋₂₀ alkenyl, for example, C₂alkenyl (e.g., vinyl) and R^(1a), R^(3a), R^(4a), R^(5a), R^(6a),R^(8a), R^(9a) and R^(10a) are each C₁₋₂₀ alkyl, for example, C₁ alkyl(e.g., methyl). In some embodiments, the low viscosityorganopolysiloxane is vinyl terminated. In other embodiments, the lowviscosity organopolysiloxane is vinyl terminated polydimethylsiloxane.

In some embodiments, the low viscosity organopolysiloxane has a weightpercent of vinyl of between about 0.010 and about 0.30, for example,between about 0.020 and about 0.29, between about 0.030 and about 0.28,between about 0.040 and about 0.27, between about 0.050 and about 0.26,between about 0.060 between about 0.25, between about 0.070 and about0.24, between about 0.080 and about 0.23, or between about 0.090 andabout 0.22. In some embodiments, the low viscosity organopolysiloxanehas a weight percent of vinyl of between about 0.18 and about 0.26.

In other embodiments, the low viscosity organopolysiloxane has a vinylequivalent per kilogram of between about 0.010 and about 0.100, forexample, between about 0.015 and about 0.090, between about 0.020 andabout 0.080, between about 0.025 and about 0.070, between about 0.030and about 0.060 or between about 0.040 and about 0.050. In someembodiments, the low viscosity organopolysiloxane has a vinyl equivalentper kilogram of between about 0.030 and about 0.040.

In other embodiments, the low viscosity organopolysiloxane has onaverage at least two vinyl units per low viscosity organopolysiloxane.In one embodiment, the monomer unit including a vinyl moiety are spacedthroughout the polymer. In one embodiment, the vinyl-containing monomerunit is spaced about 850 monomer units away from anothervinyl-containing monomer unit or a vinyl-containing terminal cap. Forexample, the vinyl units in the low viscosity organopolysiloxanes areseparated by 450, 550, 650, 750, 800, 850, 950, 1050, 1150, 1250, or1350 monomer units.

In some embodiments, the low viscosity organopolysiloxane is selectedfrom: vinyl terminated polydimethylsiloxane; vinyl terminateddiphenylsiloxane-dimethylsiloxane copolymers; vinyl terminatedpolyphenylmethylsiloxane, vinylphenylmethyl terminatedvinylphenylsiloxane-phenylmethylsiloxane copolymer; vinyl terminatedtrifluoropropylmethylsiloxane-dimethylsiloxane copolymer; vinylterminated diethylsiloxane-dimethylsiloxane copolymer;vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxyterminated; vinylmethylsiloxane-dimethylsiloxane copolymers, silanolterminated; vinylmethylsiloxane-dimethylsiloxane copolymers, vinylterminated; vinyl gums; vinylmethylsiloxane homopolymers; vinylT-structure polymers; monovinyl terminated polydimethylsiloxanes;vinylmethylsiloxane terpolymers; vinylmethoxysilane homopolymers andcombinations thereof.

In some embodiments, the organopolysiloxane is a compound of formulaIIb;

wherein R^(1c), R^(3c), R^(4c), R^(5c), R^(6c), R^(8c), R^(9c) andR^(10c) are each independently selected from hydrogen, C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxyl and e and f areeach independently an integer from between 10 and about 6000. In oneembodiment, R^(1c), R^(3c), R^(4c), R^(5c), R^(6c), R^(8c), R^(9c) andR^(10c) are alkyl (e.g., C₁ alkyl, such as methyl). In some embodiments,the sum of e and f is an integer from about 1000 to about 8000; fromabout 1300 to about 2700; from about 1500 to about 2700; from about 1600to about 2600; from about 1600 to about 2500; from about 1700 to about2500; from about 1800 to about 2400; from about 1600 to about 2300; fromabout 1900 to about 2300; from about 2000 to about 2200; from about 2050to about 2150; from about 2100.

In some embodiments, the organopolysiloxane is a compound of formulaIIc:

wherein R^(1d), R^(3d), R^(4d), R^(5d), R^(6d), R^(8d), R^(9d) andR^(10d) are each independently selected from hydrogen, C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxyl and g and j areeach independently an integer from between 10 and about 6000. In oneembodiment, R^(1d), R^(3d), R^(4d), R^(5d), R^(6d), R^(8d), R^(9d) andR^(10d) are alkyl (e.g., C₁ alkyl, such as methyl). In some embodiments,the sum of g and j is an integer from about 200 to about 1100; fromabout 600 to about 1100; from about 700 to about 1000; from about 800 toabout 900; from about 825 to about 875; from about 850; from about 200to about 800; from about 225 to about 700; from about 250 to about 600;from about 275 to about 500; from about 300 to about 400; from about 350to about 400; from about 375. In some embodiments, the sum of g and j isan integer from about 850.

In some embodiments, the reactive constituent comprises at least onehydride functionalized polysiloxane. The language “hydridefunctionalized polysiloxane” includes compounds of formula III:

wherein R^(1b), R^(2b), R^(3b), R^(4b), R^(5b), R^(6b), R^(7b), R^(8b),R^(9b) and R^(10b) are each independently selected from hydrogen, C₁₋₂₀alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxy and m and nare each independently an integer from between 10 and about 6000,provided that at least one of R^(1b), R^(2b), R^(3b), R^(4b), R^(5b),R^(6b), R^(7b), R^(8b), R^(9b) and R^(10b) is hydrogen. In someembodiments, at least one of R^(1b), R^(2b), R^(3b), R^(4b), R^(5b),R^(6b), R^(7b), R^(8b), R^(9b) and R^(10b) is hydrogen and the remainderare C₁₋₂₀ alkyl. In some embodiments, at least two of R^(1b), R^(2b),R^(3b), R^(4b), R^(5b), R^(6b), R^(7b), R^(8b), R^(9b) and R^(10b) arehydrogen (e.g., two Si—H units per functionalized hydride polysiloxanemolecule). In other embodiments, at least three of R^(1b), R^(2b),R^(3b), R^(4b), R^(5b), R^(6b), R^(7b), R^(8b), R^(9b) and R^(10b) arehydrogen (e.g., three Si—H units per functionalized hydride polysiloxanemolecule), in some embodiments, at least two of R^(1b), R^(2b), R^(3b),R^(4b), R^(5b), R^(6b), R^(7b), R^(8b), R^(9b) and R^(10b) are hydrogen(e.g., two Si—H units per functionalized hydride polysiloxane molecule)and the remainder are C₁₋₂₀ alkyl. In other embodiments, at least threeof R^(1b), R^(2b), R^(3b), R^(4b), R^(5b), R^(6b), R^(7b), R^(8b),R^(9b) and R^(10b) are hydrogen (e.g., three Si—H units perfunctionalized hydride polysiloxane molecule) and the remainder areC₁₋₂₀ alkyl. In some embodiments, at least two of R^(4b), R^(5b), R^(9b)and R^(10b) are hydrogen (e.g., two Si—H units per functionalizedhydride polysiloxane molecule) and the remainder are C₁₋₂₀ alkyl. Inother embodiments, at least three of R^(4b), R^(5b), R^(9b) and R^(10b)are hydrogen (e.g., three Si—H units per functionalized hydridepolysiloxane molecule) and the remainder are C₁₋₂₀ alkyl.

In one embodiment, at least greater than two monomer units of formulaIII include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, and R¹⁹ ishydrogen). For example, on average 2 to 15 monomer units of formula IIIinclude a Si—H unit. In one embodiment, at least two monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In one embodiment, at least three monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In one embodiment, at least four monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In one embodiment, at least five monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In one embodiment, at least six monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In one embodiment, at least seven monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In one embodiment, at least eight monomer units offormula III include a —Si—H unit (e.g. one or more of R¹¹, R¹², R¹⁸, andR¹⁹ is hydrogen). In a specific embodiment, the non Si—H positions mayinclude a Si-(alkyl) or Si-(vinyl) unit. In a specific embodiment, thenon-Si—H positions are Si—CH₃. In one embodiment, the Si—H units in thehydride-functionalized organopolysiloxanes are separated by 5, 10, 15,20, 25, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 100, 125, 150,or 200 monomer units.

In one aspect of any one of the above embodiments, the sum of m and n isan integer from about 10 to about 1300; from about 10 to about 1100;from about 10 to about 600; from about 15 to about 500; from about 15 toabout 400; from about 20 to about 300; from about 20 to about 200; fromabout 25 to about 100; from about 25 to about 75; from about 30 to about50; from about 40.

In some embodiments, the hydride functionalized polysiloxane includesSi—H units only at the terminal caps of the polymer. In someembodiments, the polysiloxane include Si—H units only in the monomerunits, but not at the terminal cap of the polymer. In other embodiments,the polysiloxane includes Si—H units at both the terminal cap or in themonomer unit of the polymer. In one embodiment, the polysiloxaneincludes two to twelve Si—H units located either at the terminal cap, orwithin the monomer unit, or a combination thereof. In one embodiment,the polysiloxane includes four to fifteen Si—H units located either atthe terminal cap, or within the monomer unit, or a combination thereof.In one embodiment, the polysiloxane includes eight Si—H units locatedeither at the terminal cap, or within the monomer unit, or a combinationthereof.

In some embodiments, the hydride functionalized polysiloxane has aviscosity of between about 5 and about 11,000 cSt or cP at 25° C., forexample, between about 10 and about 10,000 cSt or cP at 25° C., betweenabout 15 and about 5,000 cSt or cP at 25° C., between about 20 and about1,000 cSt or cP at 25° C., between about 25 and about 500 cSt or cP at25° C., between about 30 and about 100 cSt or cP at 25° C., and betweenabout 40 and about 50 cSt or cP at 25° C. In one embodiment, the hydridefunctionalized polysiloxane has a viscosity of about 45 cSt or cP at 25°C.

In some embodiments, the hydride functionalized polysiloxane has anaverage molecular weight of between about 900 and about 60,000 Da, forexample, between about 1000 and about 50,000 Da, between about 1200 andabout 25,000 Da, between about 1400 and about 20,000 Da, between about1600 and about 15,000 Da, between about 1800 and about 10,000 Da,between about 2000 and about 5000 Da, between about 2200 and about 4000Da, and between 2300 and about 2500 Da. In one embodiment, the averagemolecular weight of the hydride functionalized polysiloxane is about2400 Da.

In some embodiments, the hydride functionalized polysiloxane has apercent SiH content of between about 3 and about 45%, for example,between about 5 and about 40%, between about 10 and about 35%, betweenabout 20 and about 30%, or between about 26 and 27%. In someembodiments, the hydride functionalized polysiloxane has a percent SiHcontent of about 26%.

In some embodiments, the hydride functionalized polysiloxane has an SiHcontent of between about 0.500 mmol/g and about 10.00 mmol/g, forexample, between about 1.00 mmol/g and about 9.00 mmol/g, between about2.00 and about 8.00 mmol/g, between about 3.00 mmol/g and about 7.00mmol/g, and about 4.00 mmol/g and about 6.00 mmol/g. In one embodiment,the hydride functionalized polysiloxane has an content of between about4.00 and about 5.00 mmol/g, for example, 4.35 mmol/g.

In other embodiments, the hydride functionalized polysiloxane is alkylterminated. The language “alkyl terminated” includes hydridefunctionalized polysiloxanes of formula III in which one or both ofR^(2b) and R^(7b) are C₁₋₂₀ alkyl. In some embodiments, “alkylterminated” includes hydride functionalized polysiloxanes of formula IIIin which one, two, three, four, five or six of R^(1b), R^(2b), R^(3b),R^(6b), R^(7b) and R^(8b) are C₁₋₂₀ alkyl. In one embodiment, R^(1b),R^(2b), R^(3b), R^(4b), R^(5b), R^(6b), R^(7b), R^(8b) and R^(10b) areeach C₁₋₂₀ alkyl, for example, C₁ alkyl (e.g., methyl) and R^(9b) ishydrogen. In one embodiment, R^(1b), R^(2b), R^(3b), R^(4b), R^(5b),R^(6b), R^(7b), R^(8b) and R^(9b) are each C₁₋₂₀ alkyl, for example, C₁alkyl (e.g., methyl) and R^(10b) is hydrogen.

In some embodiments, the hydride functionalized polysiloxane, isselected from the group consisting of hydride terminatedpolydimethylsiloxane; polyphenyl-(dimethylhydrosiloxy)siloxane, hydrideterminated; methylhydrosiloxane-phenylmethylsiloxane copolymer, hydrideterminated; methylhydrosiloxane-dimethylsiloxane copolymers,trimethylsiloxy terminated; polymethylhydrosiloxanes, trimethylsiloxyterminated; polyethylhydrosiloxane, triethylsiloxane,methylhydrosiloxane-phenyloctylmethylsiloxane copolymer;methylhydrosiloxane-phenyloctylmethylsiloxane terpolymer andcombinations thereof.

In some embodiments, the reactive constituent comprises combinations ofpolymers of formulas I, II, IIa, IIb, IIc, IId, and/or III. In aspecific embodiment, the reactive constituent comprises a combination ofpolymers of formulas IIa, IIb, IIc and/or III. In a specific embodiment,the reactive constituent comprises a combination of polymers of formulasIIb, IIc and III.

In some embodiments, the reactive constituent comprises combinations ofhigh molecular weight vinyl organopolysiloxanes, low molecular weightvinyl organopolysiloxanes, and/or hydride-functionalizedorganopolysiloxanes. In one embodiment, each of the high and lowmolecular weight organopolysiloxanes includes on average at least twovinyl moieties per polymer. In a specific embodiment, each vinylorganopolysiloxane includes exactly two vinyl moieties. In oneembodiment, the ratio of the high molecular organopolysiloxane to thelow molecular weight organopolysiloxane is 2 to 3, for example 2, 2.5 or3. The ratio may be selected in order to adjust the chemical andphysical properties of the film in order to suit a specific method orpart of the body. In one embodiment, the hydride-functionalizedorganopolymer includes on average greater than two Si—H units in thepolymer. In a specific embodiment, there are 8 Si—H units perhydride-functionalized organopolysiloxane.

In some embodiments, the reactive constituent comprises combinations ofhigh molecular weight hydride-functionalized organopolysiloxanes, lowmolecular weight hydride functionalized organopolysiloxanes, and/orvinyl organopolysiloxanes. In one embodiment, each of the high and lowmolecular weight organopolysiloxanes include on average at least twoSi—H units per polymer. In a specific embodiment, eachhydride-functionalized organopolysiloxane includes exactly two Si—Hmoieties. In one embodiment, the ratio of the high molecularorganopolysiloxane to the low molecular weight organopolysiloxane is 2to 3, for example 2, 2.5 or 3. The ratio may be selected in order toadjust the chemical and physical properties of the film in order to suita specific method or part of the body. In one embodiment, the vinylorganopolymer includes on average greater than at least two vinyl unitsin the polymer. In a specific embodiment, there are 8 vinyl units pervinyl organopolysiloxane.

The language “reinforcing constituent” includes one or more constituentsof the reactive reinforcing component that provide the required physicalproperties of the film that results from the in situ reaction betweenthe reactive reinforcing component and the cross-linking component. Suchphysical properties include, for example, mechanical elements (e.g.,elasticity, durability, fracture strain, tensile strength, etc. . . . ),biocompatibility (e.g., selective breathability, adhesion, etc. . . . ),optical effects (e.g., reflectance, color, etc. . . . ) and surfacemodulation (e.g., texture, chemistry, etc. . . . ). Examples ofreinforcing, constituents include clays, (e.g., Al₂O₃, SiO₂), chalk,talc, calcite (e.g., CaCO₃), mica, barium sulfate, zirconium dioxide,zinc sulfide, zinc oxide, titanium dioxide, aluminum oxide, silicaaluminates, calcium silicates, or optionally surface treated silica(e.g., fumed silica, hydrated silica or anhydrous silica). In someembodiment reinforcing constituent is silica, for example, surfacetreated silica, such as silica treated with hexamethyldisilazane.

In some embodiments, the reinforcing constituent has a surface area ofbetween about 100 and about 300 m²/g, for example, between about 110 andabout 250 m²/g, between about 120 and about 225 m²/g, between about 130and about 200 m²/g, between about 135 and about 185 m²/g, between about160 and about 170 m²/g, and between about 164 and about 166 m²/g. In oneembodiment, the reinforcing constituent has a surface area of about160±25 m²/g.

In some embodiments, the reinforcing constituent has an average particlesize of between about 1 and about 20 μm.

In some embodiments, the reinforcing constituent is compounded with thelow viscosity and/or the high viscosity organopolysiloxane.

In some embodiments, reactive constituent and reinforcing constituentcomprise between about 20 and about 90% of the reactive reinforcingcomponent, for example, between about 40% and about 60% of the reactivereinforcing component. In some embodiments, the reactive constituent andreinforcing constituent comprise between about 45.0 and about 61.0% ofthe reactive reinforcing component, for example, about 45.0%, about45.5%, about 46.0%, about 46.5%, about 47.0%, about 47.5%, about 48.5%,about 49.0%, about 49.5%, about 50.0%, about 50.5%, about 51.0%, about51.5%, about 52.0%, about 52.5%, about 53.0%, about 53.5%, about 54.0%,about 54.5%, about 55.0%, about 55.5%, about 56.0%, about 56.5%, about57.0%, about 58.0%, about 58.5%, about 59.0%, about 59.5%, about 60.0%,or about 60.5%. In some embodiments, the reactive constituent and thereinforcing constituent comprise about 45% of the reactive reinforcingcomponent. In one embodiment, the reactive constituent and reinforcingconstituent comprise about 48.0% of the reactive reinforcing component.In some embodiments, the reactive constituent and the reinforcingconstituent comprise about 50.0% of the reactive reinforcing component.In another embodiment, the reactive constituent and reinforcingconstituent comprise about 51.0% of the reactive reinforcing component.In some embodiments, the reactive constituent and the reinforcingconstituent comprise about 51.5% of the reactive reinforcing component.In another embodiment, the reactive constituent and reinforcingconstituent comprise about 54.5% of the reactive reinforcing component.In another embodiment, the reactive constituent and reinforcingconstituent comprise about 55.0% of the reactive reinforcing component.In some embodiments, the reactive constituent and the reinforcingconstituent comprise about 59.5% of the reactive reinforcing component.In another embodiment, the reactive constituent and reinforcingconstituent comprise about 60.5% of the reactive reinforcing component.In some embodiments, the reactive constituent and reinforcingconstituent comprise between about 30.0 and about 40.0% of the reactivereinforcing component, for example, about 30.0%, about 30.5%, about31.0%, about 31.5%, about 32.0%, about 32.5%, about 33.0, about 33.5%,about 34.0%, about 34.5%, about 35.0%, about 35.5%, about 36.0%, about36.5%, about 37.0%, about 37.5%, about 38.0%, about 38.5%, about 39.0%,about 39.5%, about 40.0%. In some embodiments, the reactive constituentand reinforcing constituent comprise between about 33.0 and about 40.0%of the reactive reinforcing component

In one embodiment, the reinforcing constituent comprises between about8.0 and about 13.0% of the reactive reinforcing component, for example,about 8.5%, about 9.0%, about 9.5%, about 10.0%, about 10.5%, about11.0%, about 11.5%, about 12.0% or about 12.5%. In some embodiments, thereinforcing constituent comprises about 8.5% of the reactive reinforcingcomponent. In one embodiment, the reinforcing constituent comprisesabout 9.0% of the reactive reinforcing component. In another embodiment,the reinforcing constituent comprises about 9.5% of the reactivereinforcing component. In some embodiments, the reinforcing constituentcomprises about 10.0% of the reactive reinforcing component. In someembodiments, the reinforcing constituent comprises about 10.5% of thereactive reinforcing component. In another embodiment, the reinforcingconstituent comprises about 11.0% of the reactive reinforcing component.In another embodiment, the reinforcing constituent comprises about 12.0%of the reactive reinforcing component. In another embodiment, thereinforcing constituent comprises about 13.0% of the reactivereinforcing component.

In another embodiment, the reactive constituent comprises between about30.0 and about 60.0% of the reactive reinforcing component, for example,about 30.5%, about 31.0%, about 32.0%, about 33.0%, about 34%, about35.0%, about 36.0%, about 37.0%, about 38.0%, about 39.0%, about 40.0%,about 41.0%, about 42.0%, about 43.0%, about 44.0%, about 45.0%, about46.0%, about 47.0%, about 48.0%, about 49.0%, about 50.0%, about 51.0%,about 52.0%, about 53.0%, about 54.0%, about 55.0%, about 56.0%, about57.0%, about 58.0% or about 59.0%.

In some embodiments, the reactive reinforcing component has a viscosityof between about 5,000 and 1,000,000 cSt or cP at 25° C. In someembodiments, the reactive reinforcing component has a viscosity ofbetween about 10,000 and 10,000,000 cSt or cP at 25° C., for example,about 10,000,000, about 9,000,000, about 8,000,000, about 7,000,000,about 6,000,000, about 5,000,000, about 4,000,000, about 3,000,000 orabout 2,000,000, about 1,000,000, about 900,000, about 800,000, about700,000, about 600,000, about 500,000, about 400,000, about 300,000,about 200,000, about 100,000, about 90,000, about 80,000, about 70,000,about 60,000, about 50,000, about 40,000, about 30,000, about 20,000,about 10,000 cSt. In one embodiment, the reactive reinforcing componenthas a viscosity of about 1,000,000 cSt.

In some embodiments, the reactive reinforcing component has a vinyl tofunctional hydride (e.g., —CH═CH₂ of the one or more organopolysiloxanesto Si—H of the hydride functionalized polysiloxane) ratio of betweenabout 1:10 and about 1:100, for example, between about 1:15 and about1:90, between about 1:20 and about 1:80, between about 1:25 and about1:70, between about 1:30 and about 1:60, between about 1:35 and about1:50. In one embodiment, the reactive reinforcing component has a vinylto functional hydride ratio of about 1:40. In another embodiment, thereactive reinforcing component has a vinyl to functional hydride ratioof about 1:20. In some embodiments, the reactive reinforcing componenthas a vinyl to functional hydride ratio of about 1:15.

The language “cross-linking component” includes a component that, whenapplied to the reactive reinforcing component, catalyzes the in situformation of the body corrective film.

The term “catalyzes the in situ formation of the body corrective film”includes causing a reaction to occur between the reactive constituentsof the reactive reinforcing component, such that a body corrective filmis formed on the skin. Without being bound by theory, the cross-linkingcomponent induces a reaction between the one or more organopolysiloxanesand the hydride functionalized polysiloxane of the reactive reinforcingcomponent causing the condensation of these constituents, such that afilm is formed upon the skin.

In some embodiments, the cross-linking component comprises a metalcatalyst, for example, a platinum catalyst, a rhodium catalyst or a tincatalyst. Examples of platinum catalysts include, for example, platinumcarbonyl cyclovinylmethylsiloxane complexes, platinumdivinyltetramethyldisiloxane complexes, platinumcyclovinylmethylsiloxane complexes, platinum octanaldehyde/octanolcomplexes and combinations thereof. An example of a rhodium catalystincludes Tris (dibutylsulfide) Rhodium trichloride. Examples of tincatalysts include tin II octoate, Tin II neodecanoate, dibutyltindiisooctylmaleate, Di-n-butylbis(2,4 pentanedionate)tin,di-n-butylbutoxychlorotin, dibutyltin dilaurate, dimethyltindineodecanoate, dimethylhydroxy(oleate)tin and tin II oleate.

In some embodiments, the cross-linking component further comprises avinyl terminated organopolysiloxane (e.g., a compound of Formula I, IIIIa, IIb or IIc). In some embodiments, the amount of vinyl-terminatedpolysiloxane is a stabilizing amount of vinyl-terminated polysiloxane.The language “stabilizing amount” includes an amount that prevents thedegradation of the catalyst and/or the crosslinking component and/or thebody corrective film. In some embodiments, the stabilizing amount ofvinyl-terminated polysiloxane is less than about 50%, less than about40%, less than about 30%, less than about 20%, less than about 10%, lessthan about 5% or less than about 2%. In some embodiments, thestabilizing amount of vinyl-terminated polysiloxane is about 1%.

In some embodiments, the cross-linking component has a viscosity ofbetween about 1,000 and about 50,000 cSt or cP at 25° C.

In some embodiments, the catalyst is added as a solution and thesolution comprises between about 1.0 and about 5.0% of the cross-linkingcomponent, for example, about 1.5%, about 2.0%, about 2.5%, about 3.0%,about 3.5%, about 4.0% or about 4.5%. In one embodiment, the catalyst isabout 2.0% of the cross-linking component.

In some embodiments, the catalyst comprises between about 0.005 andabout 0.04% of the cross-linking component, for example, about 0.005,about 0.010%, about 0.015%, about 0.020%, about 0.025%, about 0.030% orabout 0.035% or about 0.040%. In one embodiment, the catalyst is about0.02% of the cross-linking component.

In some embodiments, the catalyst is present in the cross-linkingcomponent in an amount of between about 100 ppm and about 500 ppm.

In some embodiments, the reactive reinforcing component and thecross-linking component are prevented from coming into contact prior touse. The reactive reinforcing component and the cross-linking componentcan be kept from coming into contact prior to use by usual means knownto one of skill in the art. In one embodiment, the skin correctiveformulation is a two part formulation in which the reactive reinforcingcomponent and said cross-linking component are packaged in separatecontainers and mixed prior to use. In another embodiment, the reactivereinforcing component is applied to the skin first, and thecross-linking component is applied on top of the reactive reinforcingcomponent. In yet another embodiment, the cross-linking component isapplied to the skin first and the reactive reinforcing component isapplied on top of the cross-linking component. In a further embodiment,the reactive reinforcing component and the cross-linking component arepackaged together in the same container with a barrier between the twocomponents, and are mixed when the components are extracted from thecontainer.

The term “body” includes any part of the subject's body that can benefitfrom the formulations disclosed herein. Examples of the subject's bodyinclude the skin, the neck, the brow, the jowls, the eyes, the hands,the feet, the face, the cheeks, the breasts, the abdomen, the buttocks,the thighs, the back, the legs, the ankles, cellulite, fat deposits, andthe like.

The term “skin” includes the epidermis of the subject's skin, which isthe outer layer of the skin and includes the stratified squamousepithelium composed of proliferating basal and differentiated suprabasalkeratinocytes.

The term “subject” includes subjects in which the formulations disclosedherein would be appropriate for use. In one example, the subject is amammal, for example, a human. In another embodiment, the subject issuffering from wounds, or headaches such as stress headaches.

In one embodiment, the therapeutic formulation further comprises one ormore of feel modifiers, tack modifiers, spreadability enhancers,diluents, adhesion modifiers, optics modifiers, particles, volatilesiloxanes, emulsifiers, emollients, surfactants, thickeners, solvents,film formers, humectants, preservatives, pigments, cosmetic agents ortherapeutic agents. In other embodiments, the reactive reinforcingcomponent and/or the cross-linking component further comprise one ormore of feel modifiers, tack modifiers, spreadability enhancers,diluents, adhesion modifiers, optics modifiers, particles, volatilesiloxanes, emulsifiers, emollients, surfactants, thickeners, solvents,film formers, humectants, preservatives, pigments, cosmetic agents ortherapeutic agents. One of skill in the art could readily determinefurther appropriate additives based on the INCI dictionary, which isincorporated herein by reference in its entirety.

Examples of cosmetic or therapeutic agents include sunscreens (forexample, protecting agents) anti-aging agents, anti-acne agents,anti-wrinkle agents, spot reducers, moisturizers, anti-oxidants,vitamins.

In some embodiments, the emulsifier is SIMULGEL™.

In some embodiments, the composition or film is administered first,followed by administration of the one or more additional cosmetic ortherapeutic agents. In some embodiments, the composition or film isadministered after the one or more additional cosmetic or therapeuticagents. In some embodiments, the film and the one or more additionalcosmetic or therapeutic agents are administered substantially at thesame time. In some embodiments, the composition or film is used todeliver the one or more additional cosmetic or therapeutic agents.

In some embodiments, a finishing formulation may be applied to thetherapeutic formulation during or after formation of the film on thebody. The term “finishing formulation” includes a composition comprisingcomponents that provide a desired tactile sensation or a desiredaesthetic look to the film after formation. For example, the finishingformulation may provide a silky, soft and/or smooth tactile sensation ora dewy, fresh, matte, shiny or luminescent aesthetic look afterapplication to the film.

In some embodiments, the finishing formulation comprises one or more ofoils, esters or ethers, for example, triglycerides, PPG-3 benzyl ethermyristate, Schercemol DISD ester, or particles, for example, nylon,silica and silicone elastomer beads. In some embodiments, the one ormore of these components comprise from about 0.5% to about 100% of thefinishing formulation.

In some embodiments, the finishing formulation is a cream, spray, foam,ointment, serum, gel or powder.

In some embodiments, the finishing formulation further comprises one ormore f feel modifiers, tack modifiers, spreadability enhancers,diluents, adhesion modifiers, optics modifiers, particles, volatilesiloxanes, emulsifiers, emollients, surfactants, thickeners, solvents,film formers, humectants, preservatives, pigments, dyes (e.g.,fluorescent dyes), cosmetic agents or therapeutic agents.

In some embodiments, the films and formulations described hereincomprise one or more pigments. The include natural or non-naturalcoloring agents or dyes. In one embodiment, the pigments are fluorescentdyes.

In some embodiments, the films and formulation further comprise apigment dispersion formulation. The language “pigment dispersionformulation” includes a formulations that are capable of providing oneor more pigments to the films or formulations as a separate component ofthe formulation or film. In some embodiments, the pigment dispersionformulation allows for an even distribution of the pigment in the filmsand formulations. In some embodiments, the pigment dispersionformulation comprises at least one reactive constituent. In someembodiments, the pigment dispersion formulation comprises at least onereinforcing constituent. In some embodiments, the pigment dispersionformulation comprises one or more of feel modifiers, tack modifiers,spreadability enhancers, diluents, adhesion modifiers, optics modifiers,particles, volatile siloxanes, emulsifiers, emollients, surfactantsthickeners, solvents, film formers, humectants, preservatives, pigments,cosmetic agents or therapeutic agents. In other embodiments, thereactive reinforcing component and/or the cross-linking componentfurther comprise one or more of feel modifiers, tack modifiers,spreadability enhancers, diluents, adhesion modifiers, optics modifiers,particles, volatile siloxanes, emulsifiers, emollients, surfactants,thickeners, solvents, film formers, humectants, preservatives, pigments,cosmetic agents or therapeutic agents.

In some embodiments, the pigment dispersion formulation is applied priorto or after the application of the reactive reinforcing component to theskin. In some embodiments, the pigment dispersion formulation is appliedprior to or after the application of the cross-linking component to theskin. In some embodiments, the pigment dispersion formulation is appliedin between the application of the reactive reinforcing component and thecross-linking component to the skin.

In some embodiments, the pigment dispersion formulation may be appliedto skin that has not been subjected to the application of a therapeuticformulation or film. For example, a subject may apply the pigmentdispersion formulation to the skin in the area around the therapeuticfilm or formulation, or the subject may apply the pigment formulation tothe skin in lieu of applying the therapeutic film or formulation.

The terms “apply,” “applied” and “application” includes methods toadminister the formulations disclosed herein to a subject's body, suchas application by fingers, brush, cotton ball, pad, spray, sponge,cotton swab, roll-on and the like. One of skill in the art can readilydetermine appropriate methods to apply the formulations disclosedherein.

In some embodiments, the invention pertains, at least in part, to a kitcomprising a therapeutic formulation comprising a reactive reinforcingcomponent and a cross-linking component. In some embodiments, the kit isa multi-compartment kit comprising at least two compartments in whichone compartment comprises the reactive reinforcing component and thesecond compartment comprises the cross linking component. In someembodiments, the kit further comprises instructions for use of the kit,one or more brushes, one or more swabs, a film removing cleanser or amirror. In some embodiments, the kit further comprises one or morefinishing formulations.

In some embodiments, the invention pertains, at least in part, to atherapeutic film prepared by a process comprising the steps of applyinga reactive reinforcing component to the body; and applying across-linking, component to the reactive reinforcing component, in whichthe cross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component.

In some embodiments, the invention pertains, at least in part, to atherapeutic film prepared by a process comprising the steps of applyinga cross-linking component to the body; and applying a reactivereinforcing component to the cross-linking component, in which thecross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component.

In some embodiments, the therapeutic film has an appearance of naturalskin upon application to the skin. The language “appearance of naturalskin” includes the perception that the therapeutic film, when applied tothe skin, has the look, feel and texture of real skin and that the filmtreated skin has the physical properties (e.g., the elasticity andstiffness) of real (e.g., live) skin. A trained observer and/or atechnician would be able to determine whether the film upon applicationto the body has the appearance of natural skin. For example, a trainedobserver would be able to determine whether the film, upon applicationto the body, appears excessively shiny, as described in Example 3, orwhether the film appears not to move with the underlying musculature ofthe skin by, for example, breaking, buckling or deforming, in responseto natural skin motion.

A technician would be able to determine whether the film has theappearance of natural skin upon application to the body. For example,the elasticity and stiffness of skin, with or without the therapeuticfilm applied to it, can be assessed by a wide variety of methods (Agacheet al., Arch. Dermatol. Rev., 269 (1980) 221, the teachings of which areincorporated herein by reference). For example, the DermaLab suction cupinstrument provides one common method to assess the mechanicalproperties of skin, and has previously shown younger skin to be lessstiff and more elastic than aged skin (Grahame et al. Clinical Science39 (1970) 223-238, the teachings of which are incorporated herein byreference). With this method, the stiffness of the skin is indicated bythe Young's Modulus, a measure calculated by the instrument based on thepressure required to suck skin up a predetermined distance.

In some embodiments, the Young's Modulus of the skin treated with atherapeutic formulation is reduced by between about 5% to about 70%, forexample, between about 30% and about 60%, or between about 40% and about50% compared to untreated skin. In some embodiments, the Young's Modulusof skin treated with a therapeutic formulation is reduced by betweenabout 5% and about 25% compared to untreated skin.

The elasticity of the skin is determined by the skin retraction time.The retraction time is obtained by measuring the time it takes for theskin to drop a predetermined distance towards its natural position,after the suction pressure is removed. In some embodiments, theretraction time of skin treated with a therapeutic formulation isdecreased by between about 5% and about 75%, for example, between about30% and about 60%, or about 50% and about 65% when compared to untreatedskin. In some embodiments, the retraction time of skin treated with atherapeutic formulation is decreased by between about 5% and about 10%compared to untreated skin. In some embodiments, the retraction time ofthe skin treated with the film approaches the retraction time of thefilm alone.

The skin of the bicep and hand was evaluated before and after thetherapeutic treatment was applied, as shown in FIGS. 1 and 2. TheDermaLab results confirmed that the skin was less stiff (FIG. 1) andmore elastic (FIG. 2) after product application. The observed reductionin stiffness and the increase in skin elasticity are consistent withskin being more youthful.

The language “the film is formed” and “film formation” includes theresults of the polymerization reaction that occurs upon the interactionof the reactive reinforcing component and the cross-linking component.Without being bound by theory, film formation is characterized by aphase transition from the viscous sol state of a mixture to that of acontinuous interconnected polymer state of film.

A technician could determine when the film is formed on the body byusing routine methods. For example, rheological measurements using,small amplitude oscillatory shear can determine the continuous evolutionof the viscoelastic properties, such as elastic modulus (G′), theviscous modulus (G″) and the loss of tangent (tan δ) of the reactingmixture continuously through the film formation process. In someembodiments, the rheometer can be used to determine the cross over timebetween G′ and G″ and the time when tan δ becomes frequency independent,which is a measure of film formation. In some embodiments, the film isformed within at least about five minutes, for example, within about oneminute, about two minutes, about three minutes or about four minutes. Insome embodiments, the film is formed within at least about 10 secondsand about 3 minutes.

In some embodiments, the skin or therapeutic film has a Young's Modulus(e.g., tensile strength) of between about 0.01 and about 1 MPa, asillustrated in Example 1.

In some embodiments, the fracture strain of the skin or body correctivefilm has a fracture strain of at least about 150%, as measured byExample 1.

In some embodiments, the therapeutic film has a leather adhesive forceof greater than about 20 N/mm, for example, greater than about 25 N/mm,greater than about 30 N/mm, greater than about 35 N/mm, greater thanabout 40 N/mm, greater than about 45 N/mm, greater than about 50 N/mm,greater than about 55 N/mm, greater than about 60 N/mm, greater thanabout 65 N/mm, greater than about 70 N/mm, greater than about 75 N/mm,or greater than about 80 N/mm, as determined by the leather adhesiontest illustrated in Example 2. In one embodiment, the leather adhesiveforce is between about 50 and about 80 N/mm, as determined by theleather adhesion test illustrated in Example 2.

In some embodiments, the therapeutic film has a hysteresis of less thanabout 10% for example, least than about 9%, less than about 8%, lessthan about 7%, less than about 6%, less than about 5%, less than about4%, less than about 3%, less than about 2%, less than 1% or about 0%.

In some embodiments, the therapeutic film is between about 10 μm andabout 1500 μm thick, for example, between about 50 μm and about 500 μmthick. In some embodiments, the film is less than about 100 μm thick.The film thickness may be measured by methods known to one of skill inthe art, for example, by the combination of calipers and a calibratedmicroscope. The thickness of the film may also be digitally measuredfrom a micrograph of the film cross-section. The microscope calibrationallows for the conversion of measured pixelar distance into metricdistance units.

In some embodiments, the therapeutic film shrinks by less than betweenabout 1 and 30%, for example, between about 1 to about 15%. The amountof shrinking may be determined by methods known to one of skill in theart, for example, by the Croll method (Croll, S. G. J. Coatings Tech. 52(1980) 35, the teachings of which are incorporated herein by reference).In this method the film is used to coat one side of a thin flexiblesubstrate. The amount of curve developed in the substrate due to theshrinking of the coating is used to calculate the magnitude of shrinkingof the coating (Francis et al., J Mater Sci 2002; 37:4717-31, theteachings of which are incorporated herein by reference.)

In some embodiments, the therapeutic films are physiologically stable.The language “physiologically stable” includes the durability of thefilm upon exposure to normal skin conditions, for example, humidity,tears, sweat or sebum. The physiological stability may be determined bymethods typically used by one of ordinary skill in the art, such as anuptake test, which measures the change in weight of the film afterexposure to a physiological factor. For example, the uptake test mayemploy a formulation of simulated sweat (e.g., 1× phosphate bufferedsaline solution) or simulated sebum (e.g., 25% wax monoesters, 41%triglycerides, 16% fret fatty acids and 12% squalene). In someembodiments, the weight of the film increases by less than about 10%,for example, less than about 9%, less than about 8%, less than about 7%,less than about 6% less than about 5%, less than 4%, less than 3%, lessthan 2%, less than 1% or exhibits no increase upon exposure to humidity,tears, sweat or sebum.

In some embodiments, the invention pertains, at least in part, tomethods for treating wounds, comprising applying to a wound on a subjecta formulation comprising a) a first reactive reinforcing component; andb) a second cross-linking component; wherein the cross-linking componentcatalyzes an in situ cross-linking of the reactive reinforcingcomponent, such that a film is formed on the on the wound, therebytreating the wound. The language “treating a wound” includes protectingthe wound from damage while healing, for example, by providing a barrierfrom environmental elements, such as bacteria, viruses, dirt and thelike. In some embodiments, the wound is the site of a skin biopsy. Insome embodiments, the wound is not a topical disorder, such as lichensimplex chronicus, cutaneous lupus, psoriasis, eczema, acne,hypertrophic scars, warts or chronic dry skin.

In one embodiment, the invention pertains, at least in part, to methodsfor preventing a wound from occurring, comprising applying to the skinof a subject a formulation comprising a) a first reactive reinforcingcomponent; and b) a second cross-linking component; in which thecross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component, such that a film is formed on the on thewound, thereby preventing the occurrence of the wound. The language“preventing a wound from occurring” includes inhibiting or impeding theformation of a wound, for example, a wound obtained as a result ofenvironmental exposure (e.g., sun, wind or cold, which may causesunburn, windburn, dryness or hypothermia) or from mechanical injury(e.g., from rubbing between an external surface and the skin, which mycause irritation of the skin and/or blisters).

In some embodiments, the invention pertains, at least in part, to amethod for delivering an agent to a subject in need thereof, comprisingapplying to the subject's skin a formulation comprising a) a firstreactive reinforcing component optionally comprising one or more agents;and b) a second cross-linking component optionally comprising one ormore agents; in which the cross-linking component catalyzes an in situcross-linking of the reactive reinforcing component such that a film isformed on the skin, thereby delivering the agent to the subject. Thelanguage “delivering an agent” includes releasing an agent (e.g., acosmetic or therapeutic agent) to the skin of subject upon formation ofthe film on the subject's skin. In some embodiments, the agent isdelivered in one portion, or the agent is formulated to be delivered ina time-release manner. Examples of agents include cosmetic agents andtherapeutic agents.

In some embodiments, the invention pertains, at least in part, tomethods for treating a headache in a subject comprising said subject'sbrow a formulation comprising applying to an appropriate area of thesubject's skin a formulation in an amount effective to lift thesubject's skin the formulation comprising a) a first reactivereinforcing component and b) a second cross-linking component in whichthe cross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component such that a film is formed on the skin,thereby treating the headache by lifting the skin.

A headache is pain anywhere in the head or neck of a subject. The term“headache” includes both primary (e.g. a headache without a organic orstructural etiology, for example, tension headaches, migraines, clusterheadaches) and secondary (e.g. a headache caused by an injury ordisorder, for example, a stroke or glaucoma). In a specific embodiment,a headache is a stress or tension headache.

The language “treating a headache” includes reducing, alleviating orameliorating one or more symptoms of a headache, for example, painaround the head and/or neck. In one embodiment, the headache is a stressheadache. In some embodiments, the skin is facial skin (e.g., the skinaround the eyes, the skin on the brow or the skin surrounding the lips)or neck skin. In some embodiments, upon application of the therapeuticformulation, the body or skin is lifted by about 5%, about 10%, about15%, about 20%, about 25%, about 30%, about 35%, about 40% or by about50% compared to the subject's untreated body or skin. In someembodiments, the body or skin is lifted by about 1 mm, about 2 mm, about3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about9 mm, about 1 cm, about 1.5 cm, about 2.0 cm, about 2.5 cm, about 3.0cm, about 3.5 cm, about 4.0 cm, about 4.5 cm, about 5.0 cm, about 5.5cm, about 6.0 cm, about 6.5 cm, about 7.0 cm, about 7.5 cm, about 8.0cm, about 8.5 cm, about 9.0 cm, about 9.5 cm or about 10 cm uponapplication of the body corrective film.

In some embodiments, the invention pertains, at least in part, to atherapeutic formulation for application to a subject's body, comprisingat least one preselected function modulating component, wherein saidcomposition forms a therapeutic film upon application to the subject'sbody.

The term “preselected” includes components that are chosen prior to thepreparation of the formulation. For example, the components may bechosen during the manufacturing process to create a specificformulation. Alternatively, the components may be chosen by the subjectprior to application of the formulation.

The language “function modulating component” includes components thatallow the therapeutic formulations to be selectively adjusted for aparticular use of the film (e.g., reducing the appearance of wrinkles,minimizing shine, masking pores, etc. . . . ). The function modulatingcomponent or components may be selected based on the physical propertiesof the film that are necessary to be effectively applied for aparticular use of the film. For example, if the formulation will be usedto minimize shine, the modulus should be low relative to the values ofthe other physical properties of the resulting film.

In some embodiments, the invention pertains, at least in part, to atherapeutic formulation that targets a treatment area on a subject'sbody, comprising at least one preselected treatment specific component,wherein said composition forms a therapeutic film upon application tothe target treatment area on the subject's body.

The language “target treatment area” includes an area of the body wherethe formulation is meant to be applied.

The language “treatment specific component” includes components thatallow the therapeutic formulations to be selectively adjusted for atarget treatment area on the body (e.g., under the eye, forehead, lips,buttocks, neck, etc. . . . ). The treatment specific component orcomponents may be selected based on the physical properties of the filmthat results from the formulations that are necessary to be effectivelyapplied to a target treatment area, as shown in Table 1. For example, ifthe target treatment area is under the eye, the modulus should be lowrelative to the values of the other physical properties of the resultingfilm.

TABLE 1 Target Treatment Elas- Matte Area Modulus ticity ElongationAdhesion Finish Texture Under the Low High Medium High High High eyeForehead High High Medium High High High Lips Medium High High High LowLow

Examples of function modulating components and treatment specificcomponents include a stiffness component, an elasticity component, anelongation component, an adhesive component, a matte component and atextural component.

The language “stiffness component” includes components that modulate theflexibility of the resulting film, which is determined by measuring theYoung's Modulus of the film (see Example 2). Examples of stiffnesscomponents include the reactive constituent (e.g., organopolysiloxaneand/or hydride functionalized polysiloxane) and the reinforcingconstituent.

The language “elasticity component” includes components that modulatethe recoil of the resulting film, which is determined by measuring thehysteresis, and includes, for example, the reinforcing constituent.

The language “elongation component” includes components that modulatethe stretch of the resulting film, which is determined by measuring thepercent elongation to yield. Examples of elongation components includethe reactive, constituent (e.g., organopolysiloxane and/or hydridefunctionalized polysiloxane) and the reinforcing constituent.

The language “adhesion component” includes components that modulate theadherence of the resulting film to the skin, as measured by the leatheradhesive test (see Example 2). Examples of adhesion components includethe reactive constituent (e.g., organopolysiloxane and/or hydridefunctionalized polysiloxane) and the reinforcing constituent.

The language “matte component” includes components that modulate thegloss of the resulting film, as measured by determining the shine of theresulting film (see Example 3). Examples of matte components include thereinforcing constituent and light scattering particles.

The language “textural component” includes components that modulate thetexture of the film so that the resulting film has the look and feel ofnatural skin, and is measured by determining the friction of the film.One of skill in the art can readily determine methods to measure thefriction of the film, for example, by pressing in and dragging acantilever across the surface and recording the resisting force. Higherfriction corresponds to higher recorded force and rougher surfaces tendto have higher friction.

In some embodiments, the invention pertains, at least in part, to a filmremoving cleanser for use in removing a therapeutic film, wherein saidfilm is prepared by a process comprising the steps of a) applying areactive reinforcing component to skin; and b) applying a cross-linkingcomponent to said reactive reinforcing component, wherein saidcross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component.

In other embodiments, the invention pertains, at least in part, to afilm removing cleanser comprising a film wetting component, apenetration component, a film swelling component and a film releasecomponent.

The language “film removing cleanser” includes a cosmetic formulationthat, when applied to a therapeutic film, breaks down the components ofthe film such that the film may be removed from the body. In someembodiments, the film cleanser removes the film by wetting the film,penetrating the film, swelling the film and releasing the film from theskin.

The language “film wetting component” includes those components of thecleanser that allow the film to absorb liquid. In some embodiments, thefilm wetting component comprises caprylyl methicone, ethyl trisiloxaneor a combination thereof.

The language “penetration component” includes those components of thecleanser that allow the cleanser to permeate the film. Examples ofpenetration components include siloxane emulsifiers, caprylyl methicone,ethyl trisiloxane or a combination thereof.

The language “film swelling component” includes components of thecleanser which cause the film to expand. Examples of film swellingcomponents include caprylyl methicone, ethyl trisiloxane, isododecane ora combination thereof.

The language “film releasing component” includes components of thecleanser that cause the film to not adhere to the skin or body of thesubject to which the film is applied. Examples of film releasingcomponents include glycols, water or a combination thereof.

In some embodiments, the cleanser disrupts the film's mechanicalintegrity. The language “disrupt the film's mechanical integrity”includes the disturbance of the mechanical features that provide thefilm its unique properties (e.g., the stiffness, elasticity, elongation,adhesion and the like).

In some embodiments, the cleanser comprises a siloxane phase, anemulsifier phase and an aqueous phase. The language “siloxane phase”includes a component of the cleanser that comprises one or moresiloxanes, for example, caprylyl methicone and ethyl trisiloxane. Insome embodiments, the siloxane phase also includes isododecane andAerogel VM2270 (Dow Corning). The language “emulsifier phase” includes acomponent of the cleanser that comprises one or more emulsifiers, forexample, siloxane emulsifiers such as lauryl PEG-9polydiethylsiloxyethyl dimethicone, PEG-35 Castor oil, or isododecaneand lauryl dimethicone/polyglycerin 3 cross polymer. The language“aqueous phase” includes a component of the cleanser that is soluble inwater, for example, water, propylene glycol, butylenes diglycol,glycerol or combinations thereof. In some embodiments, the aqueous phaseincludes MPdiol glycol, preservatives (e.g., neolone PE), opticalparticles (e.g., silica and DMPA/isophthalic acid/SMDI copolymer & Green5) and structural particles (e.g., nylon-12).

In some embodiments, the siloxane phase is about 50% of the cleanser,the emulsifier phase is about 8% of the cleanser and the aqueous phaseis about 42% of the cleanser.

In some embodiments, the invention pertains, at least in part, to amethod of cleaning a body surface having a therapeutic film, comprisingapplying an effective amount of a film dissolving cleanser to the film,such that said film dissolves. In some embodiments, the body surface isthe skin.

In some embodiments, the invention pertains, at least in part, to aformulation for repairing a therapeutic skin applied to the skin inwhich the formulation comprises a) a first reactive reinforcingcomponent and b) a second cross-linking component; wherein thecross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component such that a film is formed on the skin.

The terms “repair” and “repairing” includes ameliorating imperfectionsin the therapeutic film after formation of the film on the skin. In someembodiments, the term “repair” includes mending or patching tears, gapsor breaks in the film. In some embodiments, the term “repair” includesreplacing a portion of the film that may have been removed from theskin. In some embodiments, the term “repair” includes re-adhering orre-attaching a portion of the film that may have come loose from theskin (e.g. de-laminated from the skin). In some embodiments, the term“repair” includes swelling the edges of the tear, gap or break in thefilm to make the film more malleable, such that the film may be able tobe reshaped.

In some embodiment, the invention pertains, at least in part, to amethod for repairing a therapeutic film applied to skin by a)identifying an area of the film in need of repair; b) optionallysmoothing the edges of the film; and c) applying a formulation forrepairing the film, wherein the formulation comprises a first reactivereinforcing component and a second crosslinking component; wherein thecross-linking component catalyzes an in situ cross-linking of thereactive reinforcing component such that a film is formed on the skin,thereby repairing the therapeutic film.

The language “smoothing the edges of the film” includes removing,swabbing, swelling, brushing or grinding the edges of the film in thearea in need of repair to remove jagged or uneven portions of the film.

In some embodiments, the invention pertains to a kit comprising a firstreactive reinforcing component, and a second cross-linking component,wherein the cross-linking component catalyzes an in situ cross-linkingof the reactive reinforcing component such that a film is formed on theskin. In some embodiments, the invention pertains, at least in part, toa kit for repairing a therapeutic film in which the kit comprises aformulation comprising a) a first reactive reinforcing component and b)a second cross-linking component wherein the cross-linking componentcatalyzes an in situ cross-linking of the reactive reinforcing componentsuch that a film is formed on the skin.

In some embodiments, the kit is a multi-compartment kit comprising atleast two compartments. In some embodiments, the reactive reinforcingcomponent is in one compartment and the cross-linking component is in asecond compartment. In some embodiments, the kit further comprises oneor more brushes, one or more swabs, a film removing cleanser,instructions for use or a mirror. In some embodiments, the kit furthercomprises a pigment dispersion formulation.

EXAMPLES Example 1 Cyclic and Extension Pull Test

Sample Preparation:

For the purpose of bulk mechanical property determination, targetmaterials were cast inside dumbbell shaped molds. The dimensions of theneck of the mold were 20 mm in length, 5 mm in width and 1.5 mm indepth. The “handles” of the mold were 20 mm by 15 mm and providedadequate area to insure secure slip-free grip during testing. The molddimensions are consistent with the ASTM D638 guidelines.

Once the poured specimens were fully cured and dried, the formed sampleswere extracted from their individual molds by means of a spatula and thegeometry of the finished pieces was measured with digital calipers todetermine precise dimensions.

Mechanical Testing:

Mechanical characterization of specimens was carried out on the Instron3342 (Instron, Norwood Mass.) equipped with LOON load-cell (Instron#2519-103). Dumbbell shaped samples were mounted onto the instrument viamodified Instron 2710-101 grips which insured sample didn't slip or failinside the grips during testing. Two types of tests were performedsequentially on each sample, first the Cyclic Test followed by theExtension Pull Test. It is noted that the first test (e.g., the cyclictest) had negligible effects on the result of the second test (e.g., theextension pull test). Each test was preprogrammed into Bluehill LiteSoftware used to operate the instrument. The parameters and dataanalysis associated with each of the two tests is described below.

Cyclic Test:

In order to determine the elasticity of the materials, a cyclic test wasdesigned. The cyclic test was used to determine the most elastic (e.g.,spring-like) material and an Instant Residual Strain (I.R.S.) wasobtained from this test, as described below. Generally, the more elasticthe material, the faster it returns to its original shape afterdeformation. For perfectly elastic materials, the I.R.S. and cycle testarea approach zero, and therefore, the lower the value the better.

Prior to starting the test, a sample was mounted onto the instrumentsuch that the rectangular handle portions of the specimen and none ofthe specimen neck were fixed within the instrument grips. The instrumentgrip distance was adjusted such that the sample was at neutral extensionas indicated by the instrument force being close to zero (±0.01N).Subsequently, cyclic extension was performed at 1 mm/s to a maximumextension of 15% of initial sample length. A total of 15 cycles areexecuted and recorded. The stress strain data recorded by instrument wasexported into Excel where the reported mechanical properties werecalculated.

An Excel template was used to automatically extract a number ofparameters. The cyclic Young's Modulus as calculated as the straightline slope of the stress-strain curve of first cycle between 1% and 4%.The R squared value of the linear fit was above 0.99 or the Young'sModulus was discarded. The Instant Residual Strain (I.R.S.) wascalculated for each cycle as the strain difference between the loadingand unloading curves at half the maximum stress achieved during the 1stcycle. The I.R.S. for the first cycle as well as the average I.R.S. forthe 4th through 14th cycles were recorded. The area bound by the loadingand unloading curves of each cycle was also calculated. Good agreementwas observed between the I.R.S. and the calculated cycle area.

The majority of the materials evaluated were sufficiently flexible andelastic such that the Cyclic Test could be repeated on the same samplewithout a significant change in calculated properties. This suggeststhis test does not result in long lasting changes to the testedmaterial.

Extension Pull Test:

The Extension Pull test was used to determine the stiffness andstretchiness of a material by measuring the Young's Modulus and UltimateStrain. The Young's Modulus was utilized as a measure of materialstiffness, while the Ultimate Strain was used as a measure of materialflexibility. In order to develop a film with the appearance of skin, theYoung's Modulus should fall within a target range (e.g., 0.1-1.0 MPa),while the fracture strain (as measured by the Ultimate Strain) should besufficiently high (e.g., greater than about 150%) so that the film willnot break when being deformed by skin movement.

The sample was mounted onto the instrument such that the rectangularhandle portions of the specimen and none of the specimen neck were fixedwithin the instrument grips. The instrument grip distance was adjustedsuch that the sample was at neutral extension as indicated by theinstrument force being close to zero (±0.01N). Subsequently, extensionuntil sample failure was performed at 10 mm/s. The stress strain datarecorded by instrument during the extension was exported to Excel wherethe reported mechanical properties were calculated.

An Excel template was used to automatically extract a number ofparameters from the instrument generated data. The extension Young'sModulus (YM) as calculated as the straight line slope of thestress-strain curve between 6% and 11%. The R squared value of thelinear fit was above 0.99 or the Young's Modulus was calculated from amore linear 5% strain range on the stress strain curve. The ShearModulus (C) was determined from the same strain range as the YM. G wascalculated as the slope of the best line fit between recorded stress andα-α-2, where α is 1 plus the instantaneous strain. The Yield strain wasdetermined as the strain at which the measured stress differed by morethan 10% from the Neo-Hookean stress; the multiple of G and (α-α-2).Ultimate Stress was calculated as the maximum stress recorded during theexperiment. The mechanical property calculations presented here areconsistent with ASTM D412.

Example 2 Leather T-Peel Adhesion Test

To determine adhesiveness of the target materials, the materials werespread onto a piece of soft flexible leather 25.4 mm wide and 76.2 mmlong. The leather used as test substrate was light weight upholsteryleather (AD1100 from Leather Unlimited, Belgium Wis.). Immediately afterspreading the material onto the first piece of leather, a secondequivalent piece of leather was placed on top to sandwich a thin layerof material between the two pieces. The two pieces of leather werepressed together to leave a thin homogeneous layer of material at theinterface of the two leather substrates. The edges were wiped to removeaccess materials and the material was allowed to cure and dry to form atest specimen.

The adhesion test sample was partially pealed at one end by hand toseparate enough of the two leather substrates for effective grip byInstron 3342 mounts. Each leather substrate was secured in its owninstrument grip and an extension test was performed at a rate of 10 mm/sto peel the two substrates from each other. The force vs. time data wasrecorded by instrument during the extension and exported to Excel wherethe reported adhesive force was calculated.

An Excel template was used to automatically extract adhesive parametersfrom the instrument generated data. The sample average adhesive forcewas calculated by averaging the instantaneous force measured by theinstrument during the experiment normalized by the sample width (25.4mm). This test method was developed in accordance with ASTM D1876. Theminimum acceptable adhesion, which depends on the stiffness of thematerial and the area on which the film is placed, was approximatelygreater than 25 N/mm

Example 3 Image Analyses Measures

Shine:

In order to measure shine, either in vitro or in vivo, a light box witha light source placed at a 45° angle relative to the site being measuredwas used to create shine, and a camera, positioned such that the angleformed by a line drawn from the lens to the area being measured is 45°,was used to photograph the site. The white balance, F-stop and ISO ofthe camera were manually fixed at set values to give adequate exposureand good color temperature. One picture was taken without any diffusingelement between the light source and the site to capture the shine.Then, a diffusing surface was placed between the light source and siteand another photograph was taken (altering shutter speed such that theexposure is similar or equal to the first photograph). This photographcaptured the surface without any shine present while the firstphotograph captured the maximum amount of shine as a result of specularreflectance. These photographs were overlaid and cropped to the relevantsample area and then the diffused photograph was subtracted from themaximum shine photograph to create a photograph with only the shinehighlights present. The entire subtracted photograph was then summarizedby finding the average grey value along with the standard deviation.This average grey value was denoted as the shine value and was used tocompare the amount of specular reflectance present in each sample. Foreach sample, the camera settings for each situation (with and withoutthe diffuser) were identical.

Photo Set Up Capture:

To ensure maximum repeatability in panelist placement for everyphotograph taken for product performance evaluation, a Head PositioningSystem (HPS) was created. This HPS had two configurations: forehead-onlyevaluations and a whole face evaluation. In both configurations, a model819 series table clamped chin-rest from Applied Science Laboratories(ASL) was used as a base to mount the two different configurations to atable. Two cameras were used to capture the subject from two differentangles. The first camera (normal shot) was positioned face-on such thatline of the lens through the camera was positioned relative to the planeof the subject's face at an angle of approximately 90°. A second camera(45° shot) was positioned to the subject's left such that the line ofthe lens through the camera was positioned relative to the plane of thesubject's face at an angle of approximately 45° capturing primarily theleft side of the subject's face. The position of the cameras relative tothe chin-rest was kept fixed. In the first configuration, an ASLcheek-rest (819-2155) was mounted to the ASL chin-rest. In this setup,the panelist's head was positioned such that the line formed from thecenter of the camera lens to the area of evaluation is normal to thearea of evaluation on the forehead. In the second configuration, an ASLforehead-rest (819-2150) was attached to the chin-rest. In this setup,the chin-rest cup was positioned such that the horizontal bar on theforehead-rest was situated at the panelist's horizontal hairline,maximizing the area of evaluation in every photograph.

Lighting for the photography consisted of two Calumet Quattrofluorescent lamps (CF0003) with four Calumet 35 Watt 5500K daylightcolor temperature fluorescent lights (OL2003) placed in front of and oneither side of the panelist, angled to point directly at the panelist. Aglare stop polarizing filter from Visual Pursuits, Inc. was also placedon the front of each lamp. The lights were allowed to warm up for atleast 10 minutes prior to taking any photographs. In addition to thelighting, a circular polarizing filter was used on each of the cameralenses to control the type of light in each photograph.

For each evaluation, two sets of pictures were taken for the normal shotcamera. In the first set, the camera's circular polarizing filter wasconfigured such that its polarization was parallel to the polarizationof the fluorescent lights, giving a picture that highlighted the shineas well as the fine wrinkles, pores and skin texture. In the second set,the circular polarizing filter was configured such that the polarizationwas perpendicular (or cross) to the polarization of the fluorescentlights yielding a result that eliminated all glare and shows theunderlying skin tone, discoloration, and deep wrinkles The 45° shotcamera was configured for each evaluation such that the camera'scircular polarizing filter was configured so that its polarization wasparallel to the polarization of the fluorescent lights, giving a picturethat highlighted the shine as well as fine wrinkles, pores and skintexture.

Brow-Lift Measure of Photo:

To measure the brow height of a photograph, a photograph was obtainedusing the method of photo capture previously described above. A “canthusline” was then drawn on the photograph from the medial to the lateralcanthus on each eye. This canthus line was used as a base from which thebrow height was measured. The eyebrow was isolated from the image byapplying valley detection, edge detection and thresholding graphicaloperations on the image. Within one experiment, the parameters forvalley and edge detection and thresholding were constant so that thesame portions of the eyebrow from each image series was the same. Toaccurately isolate the eyebrow, these parameters were changed to accountfor differences in photographic exposure between experiments and skinand brow colors between panelists. From these methods, a binary mask wascreated which was then further manipulated in order to ensure only theeyebrows were isolated in the picture. For overall height changemeasurements, the center of mass of each eyebrow was then determinedfrom its binary mask. The parameters for the binary operations andcenter of mass determination were always kept constant. The height ofeach brow was the normal from its center of mass to its correspondingcanthus line. This method measured overall height change but did notcapture the magnitude of change for severe arching or angling whereportions were raised and portions were lowered. For such cases, insteadof measuring the brow's center of mass, the heights of the brow normalto the canthus line at its left and right edges and at its center weredetermined from the binary mask.

Redness Reduction Photo Measure:

Photographs are obtained of the panelist using the photographic setuppreviously described. Comparisons of redness are only done onphotographs taken within the same experiment because the exposure, andlight and face positioning are only constant within a single experiment.After the series of photographs in the experiment are taken, thecross-polarized pictures are overlaid such that the area to be evaluatedfor redness reduction remains as fixed as is possible between eachimage. Using graphical manipulation software, the L*a*b* channels in theCIELAB colorspace are created for each image in the series. The L* valuerepresents the degree of illumination, while a* and b* define thechromaticity. Specifically, a* represents the degree of redness(+values) or greenness (−values). The intensity of the red color squareon the color card in the baseline photograph's a* channel is then usedto normalize the subsequent images by adjusting the intensity of thesubsequent image a* channels until the a* values within the red colorsquare on the color cards in those images equals the baseline value. Thearea of evaluation is then cropped out of the photographs. Rednessreduction is then determined by subtracting the a* values for the areain the ‘before’ photographs from the a* values in the ‘after’photographs. A negative value from this subtraction indicates areduction in redness while a positive value indicates an increase.

Example 4 Stress Testing Methods

The mechanical durability of the materials was evaluated by creating anartificial brow lift by applying one of the following methods ofpre-tensioning the skin during product application. These methods ofpre-tensioning were used to stress the skin surface and pull the browinto a lifted position:

-   -   “brow orthogonal push,” in which a stress was applied that        originated at the eyebrow and is vectored anteriorly away from        the eyebrow at an angle that was between 80° and 100° relative        to the line of the eyebrow,    -   “corner hairline diagonal pull,” in which a stress was applied        that originated at the most anterior and lateral point on the        panelist's hairline and was vectored anteriorly away from and at        an angle between 10° and 80° relative to the line of the        eyebrow,    -   “corner hairline orthogonal pull,” in which a stress was applied        that originated at the most anterior and lateral point on the        panelist's hairline and was vectored anteriorly away from and at        an angle between 80° and 100° relative to the line of the        eyebrow,    -   “lateral hairline orthogonal push” in which a stress was applied        that originated at the most lateral point of the hairline that        was at or above the level of the eyes and was vectored        anteriorly away from at an angle between 80° and 100° relative        to the line of the eyebrow.

While the brow was held lifted by one of these stresses, the product wasapplied to the area of skin over which the tension was being applied.Once the film cured, the stress was removed and the mechanicaldurability of the film's ability to hold the tensions in the skin wasevaluated. This evaluation was achieved by measuring the degree of browlift using the methods described before and after product application.Durability of the effect was measured by allowing time, normal andexaggerated facial expressions and environmental stresses such as water,sweat, heat, sebum production and surface contact to interact with thefilm. The amount of lift was tracked at regular intervals to determinehow quickly the film's ability to hold the mechanical benefit lasted. Afilm was determined to be mechanically durable if it could withstand thestresses previously mentioned and maintain the brow lift at the leveloriginally achieved immediately after application.

Example 5 Formulations

Examples of formulations illustrating the two-step application methodare provided below. The reactive reinforcing component first step (e.g.,the treatment) includes formulations 60-140-1, 60-140-1B, 60-140-HP2, SK87/2, 60-140-LX2, SK 87/1, 48-196, 48-199, 60-211, 60-200-1N, 60-208,66-166-F, 66-167-C, 66-166-C, 66-169-3, 66-170, 79-23, 79-24b, 79-45,79-46, 79-41, 88-30-1, 83-16, 79-55a, 79-55b, 79-55c, 79-55d, 79-55e,79-55f, 79-55g, 83-54, 79-55h, 81-18, 81-19, 81-20, 81-21, 79-74, 80-23,79-88, 79-88-3A, 79-74-RD, 79-90-B, 88-70, 88-72, 88-75-2, 88-75-3,88-80, 88-85-1, 88-85-2, 88-83-V2, 88-83-V3 and 83-54 are shown below.

Components of the formulations are commercially available. The followingtable provides the generic name for any trade name used throughout thisapplication.

International Nomenclature Cosmetic Tradename Ingredient (INCI) nameAerogel VM2270 Silica Silylate Aerosil 8200 ™ or Fumed silica modifiedwith Aerosil R8200 ™ hexamethyldisilazane Andisil C1000 ™ Silicondioxide + Dimethylpolysiloxane Andisil C1300 ™ Silicon dioxide +Dimethylpolysiloxane Andisil CE-4 ™ Vinyl Dimethicone Andisil MV 2,000 ™or Vinyl Dimethicone MV2000 Andisil VS 1,000 ™ Vinyl Dimethicone AndisilVS 10,000 ™ Vinyl Dimethicone Andisil VS 165,000 ™ Vinyl Dimethicone orAndisil VS165K Andisil VS 20,000 ™ Vinyl Dimethicone Andisil VS 250 ™Vinyl Dimethicone Andisil VS 500 ™ or Vinyl Dimethicone VS500 Andisil VS65,000 ™ or Vinyl Dimethicone VS65,000 Andisil XL-11 ™ HydrogenDimethicone, SiH Functional Andisil XL-1B ™ or Hydrogen Dimethicone, SiHFunctional XL-1B Aquadispersable Rutile Titanium dioxide TitaniumDioxide ™ Barium Sulfate HL Barium Sulfate Beaver UV/FluorescentAROMATIC HETEROCYCLE Pigment Cabosperse 1030K CAB-O-SPERSE ® 1030K is anaqueous dispersion of CAB-O-SIL ® L-90, a very low surface area, fumedsilica. It is electrostatically stabilized with Potassium Hydroxide andhas an alkaline pH. Carbopol Ultrez 21 Acrylates/C10-30 Alkyl AcrylateCrosspolymer Cetiol OE Dicapryl Ether Chronosphere Optical Silica andpolyurethane-40/silica and Brite or Chronosphere polyurethane-40 andgreen 5 Opticals/Opticals Brite cremaphor EL PEG-35 Castor Oil CrodamolSTS PPG 3 Benzyl Ether Myristate DC 200 Fluid (1 cSt) Dimethicone DC2-1184 fluid (DOW Trisiloxane (and) Dimethicone CORNING ® 2-1184 FLUID)DC 556 Phenyl Trimethicone DMF5 CS dimethicone DMS-V41Poly(Dimethylsiloxane), Vinyl Terminated Dow 245 Fluid (DowCyclopentasiloxane CORNING 245 Fluid) Dow 246 Fluid (DowCyclohexasiloxane CORNING 246 Fluid) Dow 9011 ElastomerCyclopentasiloxane (and) PEG-12 Dimethicone Blend (Dow CorningCrosspolymer 9011 Elastomer Blend) Dow Corning 9011 Cyclopentasiloxane(and) PEG-12 Dimethicone Silicone Elastomer Crosspolymer Blend ™ or DowElastomer Blend 9011 Dow 9045 Elastomer Cyclopentasiloxane (and)Dimethicone Blend or Dow Corning Crosspolymer 9045 Silicone ElastomerBlend ™ Dow Corning 200 Fluid Hexamethyldisiloxane 0.65 cSt ™ DowCorning 245 Decamethylcyclopentasiloxane Fluid ™ Dow Corning 5329 PEG-12Dimethicone Dow Elastomer Blend Dimethicone (and) DimethiconeCrosspolymer 9041 or DOW CORNING ® 9041 SILICONE ELASTOMER BLEND dowanolDPM Dipropylene Glycol Methyl Ether Dri-Flow Elite BN or Aluminum StarchOctenylsuccinate (and) DRY-FLO Elite BN Boron Nitride Flo-BeadsSE-3207B ™ Ethylene-methyl methacrylate copolymer Dow Corning FZ-3196Caprylyl Methicone Ganzpearl GMP-0830 ™ Acrylates CrosspolymerGranhydrogel O ™ Water (and) Glyceryl Polyacrylate (and) 1,3- ButyleneGlycol (and) PVM/MA (and) Propylparaben (and) Methylparaben GranpowderNylon ™ Nylon-12 Gransil EP-LS ™ Polysilicone-11 (and) Laureth-12Gransurf 90 Cetyl PEG/PPG-10/1 Dimethicone Iris C12-17 Alkanes IronOxide Tint or Iron Iron Oxides Oxide Tint Mixture Isododecane mixture ofhighly branched C12 isoparaffins, mainly the2,2,4,6,6-pentamethylheptane isomer (typically c.a. 85%). Jeechem BUGL ™or Butylene Glycol Jeen BUGL Jeecide cap 5 Phenoxyethanol, CaprylylGlycol, Potassium Sorbate, Aqua, Hexylene Glycol Jeensilc CPS-312 ™Cyclomethicone Kaolin USP BC2747 Kaolin KF6013 PEG-9 Dimethicone KTZXian Vistas ™ Titanium Dioxide (And) Mica (And) Iron Oxide (C.I. 77491);chemical name: Mica (and) Titanium Dioxide (and) Ferrous Oxide LabrafacCC ™ Caprylic/Capric Triglyceride LILAC ™ (Sonneborn) C14-22 AlkaneMPDiol Methyl Propanediol Neolone PE ™ Phenoxyethanol,Methylisothiazolinone Nylon Nylon 12 Nylon 10-I2 ™ Nylon 12 (And)Isopropyl Titanium Triisostearate PC 075.3 Hydrogen Dimethicone Pinktint mix Iron Oxides Plantacare 818 UP ™ Coco-Glucoside; ChemicalDescription is “C8-16 fatty alcohol glucoside” Platinum divinyl UPACname “1,3-Diethenyl-1,1,3,3- complex (for exampletetramethyldisiloxane-platinum (1:1)”; Trade PT-50175F) name:“Platinum-divinyltetramethyldisiloxane complex”; Synonyms:Platinum(0)-1,3-divinyl- 1,1,3,3-tetramethyldisiloxane complex solution;pt(0)-1,3-divinyl-tetrame-disiloxane compl 0.100;1,3-Divinyl-1,1,3,3-tetramethyl- disiloxane-platinum (0) PMX-1184 orDimethicone and trisiloxane XIAMETER ® PMX- 1184 Silicone FluidPolyglycol P425 PPG-9 prestige pearlescent mixture of titanium and ironoxides of a beige beige color PS123-KG Hydrogen Dimethicone RM 2051 orRM 2051 Sodium Polyacrylate (and) Dimethicone (and) Thickening AgentCyclopentasiloxane (and) Trideceth-6 (and) PEG/PPG 18/18 Schercemol ™318 Ester Isopropyl Isostearate Sepiplus 400 ™ Polyacrylate 13 (and)Polyisobutene (and) Polysorbate 20 Shin Etsu KF 6038 Lauryl PEG-9Polymethylsiloxyethyl Dimethicone Shin Etsu KSG 820 LaurylDimethicone/Polyglycerin-3 Crosspolymer Silsoft 034 caprylyl methiconesilsoft ETS ethyl trisiloxane Simulgel EG ™ Sodiumacrylate/acryloyldimethyl taurate copolymer & Isohexadecane &Polysorbate 80 SIMULGEL NS Hydroxyethylacrylate/sodium acryloyldimethyltaurate copolymer & squalane & polysorbate 60 Soft Bead B or SoftEthylene/Methacrylate Copolymer Beads B Solagum AX Acacia senegal gumand xanthan gum SR 1000 Resin Trimethylsiloxysilicate Tint Iron OxidesTMF 1.5 Methyl Trimethicone Tween 20 Polysorbate 20 UCT-PS448.5Polydimethylsiloxane, Vinyldimethyl Terminated USG 102 Dimethicone/VinylDimethicone Crosspolymer Veegum Pro Tromethamine Magnesium AluminumSilicate Veegum Ultra Granules Magnesium Aluminum Silicate Velvesil125 ™ Cyclopentasiloxane (and) C30-45 Alkyl Cetearyl DimethiconeCrosspolymer Velvet Veil 310 ™ Mica (and) Silica Vitamin-A complexretinol Vitamin-C complex ascorbic acid Vitamin-E complex TocopherolXirona caribbean blue Mica, Titanium Dioxide, Silica, Tin OxideFormulation 60-140-1

Component Percent of No. Component Formulation (%) 1 DMS-V41 23.80 2Aerosil 8200 9.45 3 PS123-KG 12.00 4 UCT-PS448.5 5.55 5 Velvesil 1253.60 6 Gransil EP-LS 3.60 7 Soft Beads B 1.20 8 Sepiplus 400 1.20 9Water 27.00 10 Granhydrogel O 6.70 11 Granpowder 5.90 NylonProcedure:

Components 1-4 were hand mixed in a graduated 4-oz until mixture wasfree of white particulates. Subsequently, components 5-8 were added andthe mixture was confirmed as homogenous (Mixture A). In a separatevessel, components 9 and 10 were hand mixed until homogenous (MixtureB). Mixture B was added to Mixture A under strong agitation, provided bya 4-blade, 40 mm propeller at 550 rpm, then component 11 was added andthe mixing speed was to 1000 rpm and mix for 5 minutes. The mixture wasconfirmed as homogenous.

Formulation 60-140-1B

Component Percent of No. Component Formulation (%) 1 DMS-V41 22.60 2Aerosil 8200 8.94 3 PS123-KG 11.30 4 UCT-PS448.5 5.30 5 Velvesil 1253.42 6 Gransil EP-LS 3.42 7 Soft Beads B 1.20 8 Sepiplus 400 1.20 9Water 25.66 10 Granhydrogel O 6.36 11 Granpowder 5.60 Nylon 12 Cetiol OE5.00Procedure:

Components 1-4 were hand mixed in a graduated 4-oz and the mixture wasconfirmed as free of white particulates. Subsequently, components 5-8were added and the mixture was confirmed homogenous (Mixture A). In aseparate vessel, components 9 and 10 were hand mixed until homogenous(Mixture B). Mixture B to was added Mixture A under strong agitation,provided by a 4-blade, 40 mm propeller at 550 rpm, then components 11and 12 were added and the mixing speed was increased to 1000 rpm and mixfor 5 minutes. The mixture was confirmed as homogenous.

Formulation 60-140-HP2

Component Percent of No. Component Formulation (%) 1 UCT-PS448.5 32.97 2Aerosil 8200 12.82 3 PS123-KG 14.65 4 Velvesil 125 4.40 5 Gransil EP-LS4.40 6 Soft Beads B 1.47 7 Sepiplus 400 1.47 8 Granhydrogel O 20.63 9Granpowder 7.20 NylonProcedure:

Components 1-3 were hand mixed in a graduated 4-oz, and the mixture wasconfirmed as free of white particulates. Subsequently, components 4-7were added the mixture was confirmed homogenous (Mixture A). In aseparate vessel, component 8 was mixed until homogenous (Mixture B).Mixture B to was added Mixture A under strong agitation, provided by a4-blade, 40 mm propeller at 550 rpm, then component 9 was added and themixing speed was increased to 1000 rpm and mix for 5 minutes. Themixture was confirmed as homogeneous.

Formulation SK 87/2

Component Percent of No. Component Formulation (%) 1 DMS V41 35.00 2Aerosil 8200 11.60 3 PS123-KG 5.20 4 Velvesil 125 11.20 5 Gransil EP-LS8.70 6 Water 6.70 7 Polyvinyl alcohol 2.00 8 Granhydrogel O 8.70 9Granpowder 6.10 Nylon 10 Silsoft 034 4.80Procedure

Components 1-3 were hand mixed in a graduated 4-oz and the mixture wasconfirmed as free of white particulates. Subsequently, components 4 and5 were added and the mixture was confirmed as homogenous (Mixture A). Ina separate vessel, components 6 and 7 were hand mixed until homogenous(Mixture B). Mixture B was added to Mixture A under strong agitation,provided by a 4-blade, 40 mm propeller at 550 rpm, then components 8-10were added and the mixing speed was increased to 1000 rpm and mix for 5minutes. The mixture was confirmed as homogeneous.

Formulation 60-140-LX2

Component Percent of No. Component Formulation (%) 1 DMS V41 27.51 2Aerosil 8200 10.87 3 PS123-KG 3.47 4 UCT-PS448.5 13.41 5 Velvesil 1254.16 6 Gransil EP-LS 4.16 7 Soft Bead B 1.39 8 Sepiplus 400 1.39 9 Water21.45 10 Granhydrogel O 5.38 11 Granpowder 6.82 NylonProcedure:

Components were hand mixed 1-4 in a graduated 4-oz and the mixture wasconfirmed as free of white particulates. Subsequently, components 5-8were added and mixture was confirmed as homogenous (Mixture A). In aseparate vessel, components 9 and 10 were hand mixed until homogenous(Mixture B). Mixture B was added to Mixture A under strong agitation,provided by a 4-blade, 40 mm propeller at 550 rpm, then component 11 wasadded and the mixing speed was increased to 1000 rpm and mixed for 5minutes. The mixture was confirmed as homogeneous.

Formulation SK 87/1

Component Percent of No. Component Formulation (%) 1 DMS V41 36.90 2Aerosil 8200 12.30 3 PS123-KG 5.50 4 Velvesil 125 11.60 5 Gransil EP-LS9.10 6 Water 7.10 7 Polyvinyl alcohol 2.00 8 Granhydrogel O 9.10 9Granpowder 6.40 NylonProcedure:

Components 1-3 were hand mixed in a graduated 4-oz and the mixture wasconfirmed as free of white particulates. Subsequently, components 4 and5 were added and the mixture was confirmed as homogenous (Mixture A). Ina separate vessel, components 6 and 7 were hand mixed until homogenous(Mixture B). Mixture B was added to Mixture A under strong agitation,provided by a 4-blade, 40 mm propeller at 550 rpm, then components 8 and9 were added and the mixing speed was increased to 1000 rpm and mixedfor 5 minutes. The mixture was confirmed as homogeneous.

Formulation 48-196

Component Percent of No. Component Formulation (%) 1 Andisil VS10,00024.46 2 Andisil VS165K 3.66 3 Aerosil 8200 9.72 4 Andisil XL-11 12.33 5Velvesil 125 3.70 6 Gransil EP-LS 3.70 7 Soft Beads B 1.23 8 Sepiplus400 1.23 9 Water 27.75 10 Granhydrogel O 6.87 11 Neolone PE 0.21 12Granpowder 4.11 Nylon 13 Tint 1.03Procedure:

Components 1-3 were mixed in a graduated 4-oz with a 4-blade propellerat 1000 RPM until homogenous (Mixture A) and the mixture was confirmedas homogenous. In a separate container components 4-8 were mixed with a4-blade propeller at 750 RPM until homogenous (Mixture B). In anothercontainer, components 9-11 were mixed with a 4-blade propeller at 750RPM until homogenous (Mixture C). Mixture B was added to Mixture C understrong agitation, provided by a 4-blade, 40 mm propeller at 750 rpm,then Mixture A was added to combined Mixtures B and C drop by drop.Finally, components 12 and 13 were added and the mixing speed increasedto 1000 RPM and mix for 10 minutes. The mixture was confirmed ashomogeneous.

Formulation 48-199

Component Percent of No. Component Formulation (%) 1 Andisil VS10,00022.11 2 Andisil VS165K 3.31 3 Aerosil 8200 8.79 4 Andisil XL-11 11.15 5Velvesil 125 3.35 6 Gransil EP-LS 3.35 7 Soft Beads B 1.12 8 Sepiplus400 1.12 9 Water 25.09 10 Granhydrogel O 6.21 11 Neolone PE 0.19 12Granpowder 4.94 Nylon 13 Silsoft 034 9.29Procedure:

Components 1-3 were mixed in a graduated 4-oz with a 4-blade propellerat 1000 RPM until homogenous (Mixture A). In a separate container,components 4-8 were mixed with a 4-blade propel at 750 RPM untilhomogenous (Mixture B). In another container, components 9-11 were mixedwith a 4-blade propeller at 750 RPM until homogenous (Mixture C).Mixture B to Mixture C was added under strong agitation, provided by a4-blade, 40 mm propeller at 750 rpm, then Mixture A was added tocombined Mixtures B and C drop by drop. Finally, components 12 and 13were added and the mixing speed was added to 1000 RPM and mixed for 10minutes. The mixture was confirmed as homogeneous.

Formulation 60-211

Component Percent of No. Component Formulation (%) 1 Andisil C1000 33.662 Andisil C1300 6.73 3 Andisil XL-11 9.62 4 Velvesil 125 3.46 5 GransilEP-LS 3.46 6 Soft Beads B 1.15 7 Sepiplus 400 1.15 8 Water 25.97 9Granhydrogel O 6.42 10 Jeechem BUGL 3.85 11 Neolone PE 0.19 12Granpowder 3.85 Nylon 13 Tint 0.49Procedure:

Components 1-7 were mixed in a graduated 4-oz with a 4-blade propellerat 2000 RPM until homogenous (Mixture A). In a separate container,components 8-11 were mixed with a 4-blade propeller at 750 RPM untilhomogenous (Mixture B). Mixture B was slowly added to Mixture A understrong agitation provided by a 4-blade propeller at 2000 RPM. Components12 and 13 were added and the mixing speed was increased to 2000 RPM for5 minutes. The mixture was confirmed as homogeneous.

Formulation 60-200-1N

Component Percent of No. Component Formulation (%) 1 Andisil C1000 33.882 Andisil C1300 7.65 3 Andisil XL-11 18.03 4 SR 1000 Resin 10.93 5 Iris2.19 6 Dri-Flow Elite BN 10.93 7 Barium Sulfate HL 4.37 8 Gransil EP-LS8.74 9 Sepiplus 400 2.19 10 Neolone PE 0.55 11 Tint 0.54Procedure:

Components 1-5 were mixed in a graduated 4-oz with a 4-blade propellerat 2000 RPM until homogenous (Mixture A). Components 6-9 were then addedand mixed with a 4-blade propeller at 2000 RPM until homogenous.Components 10 and 11 were added and the mixing speed was mixed at 2000RPM until homogeneous.

Formulation 60-208

Component Percent of No. Component Formulation (%) 1 Andisil C1000 30.052 Andisil C1300 6.56 3 Andisil XL-11 22.95 4 SR 1000 Resin 10.93 5 Iris2.19 6 Dri-Flow Elite BN 10.93 7 Barium Sulfate HL 4.37 8 Gransil EP-LS8.74 9 Sepiplus 400 2.19 10 Neolone PE 0.55 11 Tint 0.54Procedure:

Components 1-5 were mixed in a graduated 4-oz with a 4-blade propellerat 2000 RPM until homogenous (Mixture A). Components 6-9 were then addedand mixed with a 4-blade propeller at 2000 RPM until homogenous.Components 10 and 11 were added and the mixing speed was mixed at 2000RPM until homogeneous.

Formulation 66-166-F

Component Percent of No. Component Formulation (%) 1 Aerosil 8200 ™8.43% 2 Andisil VS 10,000 ™ 21.22% 3 Andisil VS 165,000 ™ 3.17% 4Andisil XL11 ™ 10.34% 5 Velvesil 125 ™ 3.10% 6 Gransil EP-LS ™ 3.10% 7Flo-Beads SE-3207B ™ 1.03% 8 Sepiplus 400 ™ 1.03% 9 Water 23.28% 10Granhydrogel O ™ 5.75% 11 Neolone PE ™ 0.17% 12 Granpowder Nylon ™ 4.23%13 Ganzpearl GMP-0830 ™ 0.31% 14 Velvet Veil 310 ™ 0.21% 15Aquadispersable Rutile 0.21% Titanium Dioxide ™ 16 Yellow Iron Oxide0.09% 17 Red Iron Oxide 0.04% 18 Black Iron Oxide 0.01% 19 Dow Corning200 Fluid 14.29% 0.65 cSt ™Procedure:

Components 1-3 were mixed together as siloxane phase A. Into siloxanephase B, components 4-8 were mixed. Components 9-11 were combined as thewater phase. The water phase was slowly added to siloxane phase B andmixed until homogenous. Into this new phase, phase A was added veryslowly drop by drop. Once all of siloxane phase A was added, components12-19 were added to the formula and mix until homogenous.

Formulation 66-167-E

Component Percent of No. Component Formulation (%) 1 Aerosil 8200 ™8.36% 2 Andisil VS 10,000 ™ 21.05%  3 Andisil VS 165,000 ™ 3.15% 4Andisil XL11 ™ 10.25%  5 Velvesil 125 ™ 3.08% 6 Gransil EP-LS ™ 3.08% 7Flo-Beads SE-3207B ™ 1.02% 8 Sepiplus 400 ™ 1.02% 9 Water 23.09%  10Granhydrogel O ™ 5.70% 11 Neolone PE ™ 0.17% 12 Granpowder Nylon ™ 4.20%13 Ganzpearl GMP-0830 ™ 0.31% 14 Velvet Veil 310 ™ 0.20% 15Aquadispersable Rutile 0.20% Titanium Dioxide ™ 16 Yellow Iron Oxide0.09% 17 Red Iron Oxide 0.04% 18 Black Iron Oxide 0.01% 19 LILAC ™(Sonneborn)   2% 20 Cetyl Dimethicone   5% 21 Granhydrogel O ™   8%Procedure:

Components 1-3 were mixed together as siloxane phase A. Into siloxanephase B components 4-8 were added. Components 9-11 were combined as thewater phase. The water phase was slowly added to siloxane phase B andmixed until homogenous. Into this new phase, phase A was added veryslowly drop by drop. Once all of siloxane phase A was added, components12-21 were added to the formula and mixed until homogenous.

Formulation 66-166-C

Component Percent of No. Component Formulation (%) 1 Aerosil 8200 ™8.43% 2 Andisil VS 10,000 ™ 21.22% 3 Andisil VS 165,000 ™ 3.17% 4Andisil XL11 ™ 10.34% 5 Velvesil 125 ™ 3.10% 6 Gransil EP-LS ™ 3.10% 7Flo-Beads SE-3207B ™ 1.03% 8 Sepiplus 400 ™ 1.03% 9 Water 23.28% 10Granhydrogel O ™ 5.75% 11 Neolone PE ™ 0.17% 12 Granpowder Nylon ™ 4.23%13 Ganzpearl GMP-0830 ™ 0.31% 14 Velvet Veil 310 ™ 0.21% 15Aquadispersable Rutile 0.21% Titanium Dioxide ™ 16 Yellow Iron Oxide0.09% 17 Red Iron Oxide 0.04% 18 Black Iron Oxide 0.01% 19 GranhydrogelO ™ 14.29%Procedure:

Components 1-3 were mixed together as siloxane phase A. Into siloxanephase B components 4-8 were added. Components 9-11 were combined as thewater phase. The water phase was slowly added to siloxane phase B andmixed until homogenous. Into this new phase, phase A was very slowlyadded drop by drop. Once all of siloxane phase A was added, components12-19 was added to the formula and mixed until homogenous.

Formulation 66-169-3

Component Percent of No. Component Formulation (%) 1 Ganzpearl GMP-0.16% 0830 ™ 2 Velvet Veil 310 ™ 0.10% 3 Aquadispersable 0.10% RutileTitanium Dioxide ™ 4 Yellow Iron Oxide 0.04% 5 Red Iron Oxide 0.02% 6Black Iron Oxide 0.01% 7 Gransil EP-LS ™ 0.76% 8 Andisil XL-11 ™ 8.61% 9Gransil EP-LS ™ 2.34% 10 Andisil C1000 ™ 33.51% 11 Andisil C1300 ™ 6.67%12 Andisil XL-11 ™ 1.59% 13 Velvesil 125 ™ 3.48% 14 Flo-Beads SE- 1.15%3207B ™ 15 Sepiplus 400 ™ 1.27% 16 Water 25.18% 17 Granhydrogel O ™6.22% 18 Jeechem BUGL ™ 3.75% 19 Neolone PE ™ 0.21% 20 Granpowder 3.83%Nylon ™ 21 KTZ Xian Vistas ™ 1.00%Procedure:

Components 1-8 were mixed together and homogenized at 26,000 RPM for 10minutes. After 10 minutes, component 9 was added and homogenized againfor 10 minutes at 26,000 RPM. To this homogenized mixture, components10-15 were added and mixed with an overhead stirrer at 2,000 RPM untilhomogenous in appearance (this is the siloxane phase). In a separatecontainer, components 16-19 were mixed until homogenous to form thewater phase. The water phase was added to the siloxane phase veryslowly, with continuous stilling at 2,000 RPM. Once the water phase wascompletely mixed in, components 20 and 21 were added to the formula andmixed at 2,000 RPM until homogenous.

Formulation 66-170

Component Percent of No. Component Formulation (%) 1 Andisil C1300 ™8.92% 2 Andisil C1000 ™ 44.21% 3 Andisil XL-11 ™ 12.67% 4 Sepiplus 400 ™1.30% 5 Ganzpearl GMP-0830 ™ 0.18% 6 Velvet Veil 310 ™ 0.12% 7Aquadispersable Rutile 0.12% Titanium Dioxide ™ 8 Yellow Iron Oxide0.05% 9 Red Iron Oxide 0.02% 10 Black Iron Oxide 0.01% 11 Dow Corning9011 3.25% Silicone Elastomer Blend ™ 12 Dow Corning 9045 3.25% SiliconeElastomer Blend ™ 13 Dow Corning 245 2.62% Fluid ™ 14 Jeensilc CPS-312 ™0.65% 15 Water 9.49% 16 Plantacare 818 UP ™ 0.16% 17 Propylene Glycol6.60% 18 Glycerin 1.29% 19 Jeechem BUGL ™ 3.22% 20 Sodium Chloride 0.32%21 Nylon 10-I2 ™ 1.53%Procedure:

Components 1-10 were mixed together to create the siloxane phase A.Next, components 11-14 were mixed to create siloxane phase B. A waterphase was created by mixing components 15-20. The water phase was slowlyadded into siloxane phase B while mixing at 2,000 RPM to create phase C.Finally, phase C was mixed into siloxane phase A until homogenous.

Formulation 79-23

Component Percent of No. Component Formulation (%) 1 Andisil VS 500 ™0.72 2 Andisil MV 2000 ™ 1.02 3 Andisil VS 65,000 ™ 17.20 4 AndisilXL-1B ™ 22.52 5 Aerosil R8200 ™ 11.77 6 Ganzpearl GMP- 0.19 0830 ™ 7Velvet Veil 310 ™ 0.13 8 Aquadispersable Rutile 0.13 Titanium Dioxide ™9 Yellow Iron Oxide 0.05 10 Red Iron Oxide 0.03 11 Black Iron Oxide 0.0112 Gransil EP-LS ™ 3.59 13 Velvesil 125 ™ 3.58 14 Flo-Beads SE- 1.023207B ™ 15 Sepiplus 400 ™ 1.10 16 Water 23.72 17 Granhydrogel O ™ 6.9918 Jeechem BUGL ™ 3.50 19 Sodium Chloride 0.35 20 Neolone PE ™ 0.35 21Granpowder Nylon ™ 2.05Procedure:

Components 1-5 were combined and mixed (Mixture A) in a dual asymmetriccentrifugal mixer at 2500 RPM while confirming that the mixture was fretof white particulates. Components 6-15 were mixed into Mixture A andmixed in a dual asymmetric centrifugal mixer. Mixture A was confirmed ashomogenous. In a separate vessel, components 16 and 20 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture B).Mixture B was added to Mixture A dropwise while mixing with a 4-blade 40mm propeller at 2000 rpm and the mixture was confirmed as homogenous.Component 21 was added to the product of Mixture A and Mixture B andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-24b

Component Percent of No. Component Formulation (%) 1 Andisil VS 500 ™0.72 2 Andisil MV 2000 ™ 1.07 3 Andisil VS 65,000 ™ 17.91 4 AndisilXL-1B ™ 23.15 5 Aerosil R8200 ™ 12.12 6 Ganzpearl GMP- 0.19 0830 ™ 7Velvet Veil 310 ™ 0.13 8 Iron Oxide Tint 0.22 9 Gransil EP-LS ™ 3.70 10Velvesil 125 ™ 3.70 11 Flo-Beads SE- 1.06 3207B ™ 12 Sepiplus 400 ™ 1.1113 Water 22.31 14 Granhydrogel O ™ 6.56 15 Jeechem BUGL ™ 3.28 16 SodiumChloride 0.33 17 Neolone PE ™ 0.33 18 Granpowder Nylon ™ 2.12Procedure:

Components 4, 8 and 9 were combined and homogenized until smooth at20000 RPM. Components 1-3, 6-7, 10-12 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates were no longer visible (Mixture A). In a separate vessel,components 13-17 were mixed with a 4-blade, 40 mm propeller at 550 rpmuntil homogenous (Mixture B). Mixture B was added to Mixture A dropwisewhile mixing with a 4-blade 40 mm propeller at 2000 rpm and the mixturewas confirmed as homogenous. Component 18 was added to the product ofMixture A and Mixture B and mixed with 4-blade 40 mm propeller at 1000rpm until homogenous.

Formulation 79-45

A 2:1 blend of Formulations 60-211 and 79-24b was mixed together with a4-blade 40 mm propeller at 2000 rpm for 2 minutes.

Formulation 79-46

A 1:2 blend of Formulations 60-211 and 79-24b was mixed together with a4-blade 40 mm propeller at 2000 rpm for 2 minutes.

Formulation 79-41

A 1:5 blend of Formulations 60-211 and 79-24b was mixed together with a4-blade 40 mm propeller at 2000 rpm for 2 minutes.

Formulation 88-30-1

Component Percent of No. Component Formulation (%) 1 VS500 0.68 2 MV20001.02 3 VS65,000 17.00 4 XL-1B 21.96 5 Aerosil R 8200 11.51 6 Dow 246Fluid 10.43 7 Crodamol STS 1.15 8 83-49 12.00 9 83-50 3.39 10 Cabosperse1030K 20.87Procedure:

Ingredients 1 through 7 were mixed using a propeller blade at 275 RPM toprepare phase A. In a separate vessel components 8 through 10 weremixed, using a propeller blade at 275 RPM, to prepare phase B. Phase Bwas mixed into phase A at 275 RPM until the emulsion is uniform. Anamount of 0.01% iron oxides was added to the final formulation to impartcolor. Formulation 83-49 and 83-50 are emulsions of VS 165,000 vinylsiloxane and XL-11 hydride functionalized siloxane, respectively,containing 65% siloxanes, 8% oleth-10 surfactant, and the balance water.

Formulation 83-16

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™ 3.52 Andisil XL-11 ™ 9.76 3 Andisil VS 1,000 ™ 25.53 4 Andisil VS 165,000 ™5.12 5 Aerosil R8200 ™ 10.23 6 Velvesil 125 ™ 3.51 7 Flo-BeadsSE-3207B ™ 1.17 8 Sepiplus 400 ™ 1.22 9 Granpowder Nylon ™ 3.9 10 Water25.47 11 Granhydrogel O ™ 6.32 12 Jeechem BUGL ™ 3.97 13 Neolone PE ™0.22 14 Iron Oxide Tint 0.08 MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 9 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates were no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 10 to 13 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 14 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55a

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-11 ™ 8.17 3 Andisil VS 1,000 ™ 32.59 4 Andisil VS165,000 ™ 6.52 5 Andisil XL-11 ™ 3.04 6 Aerosil R8200 ™ 13.04 7 Sepiplus400 ™ 1.14 8 Water 21.76 9 Granhydrogel O ™ 6.40 10 Jeechem BUGL ™ 3.2011 Sodium Chloride 0.32 12 Neolone PE ™ 0.32 13 Iron Oxide Tint 0.01MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 7 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 8 to 12 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 13 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55b

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-11 ™ 8.17 3 Andisil VS 10,000 ™ 30.33 4 Andisil VS165,000 ™ 7.10 5 Andisil XL-11 ™ 5.49 6 Aerosil R8200 ™ 12.26 7 Sepiplus400 ™ 1.14 8 Water 21.76 9 Granhydrogel O ™ 6.40 10 Jeechem BUGL ™ 3.2011 Sodium Chloride 0.32 12 Neolone PE ™ 0.32 13 Iron Oxide Tint 0.01MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 7 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 8 to 12 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 13 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55c

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-1B ™ 8.17 3 Andisil VS 500 ™ 0.84 4 Andisil MV 2,000 ™1.29 5 Andisil VS 65,000 ™ 21.04 6 Andisil XL-1B ™ 17.82 7 AerosilR8200 ™ 14.20 8 Sepiplus 400 ™ 1.14 9 Water 21.76 10 Granhydrogel O ™6.40 11 Jeechem BUGL ™ 3.20 12 Sodium Chloride 0.32 13 Neolone PE ™ 0.3214 Iron Oxide Tint 0.01 MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 8 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 9 to 13 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 14 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55d

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-1B ™ 8.17 3 Andisil VS 250 ™ 1.29 4 Andisil MV 2,000 ™1.94 5 Andisil VS 20,000 ™ 24.52 6 Andisil CE-4 ™ 1.94 7 Andisil XL-1B ™0.33 8 Andisil XL-11 ™ 10.97 9 Aerosil R8200 ™ 14.20 10 Sepiplus 400 ™1.14 11 Water 21.76 12 Granhydrogel O ™ 6.40 13 Jeechem BUGL ™ 3.20 14Sodium Chloride 0.32 15 Neolone PE ™ 0.32 16 Iron Oxide Tint 0.01MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 10 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 11 to 15 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 16 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55e

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-1B ™ 8.17 3 Andisil VS 250 ™ 1.29 4 Andisil MV 2,000 ™1.94 5 Andisil VS 65,000 ™ 22.91 6 Andisil XL-1B ™ 6.78 7 AndisilXL-11 ™ 8.07 8 Aerosil R8200 ™ 14.20 9 Sepiplus 400 ™ 1.14 10 Water21.76 11 Granhydrogel O ™ 6.40 12 Jeechem BUGL ™ 3.20 13 Sodium Chloride0.32 14 Neolone PE ™ 0.32 15 Iron Oxide Tint 0.01 MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 9 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 10 to 14 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 15 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55f

Component Percent of No. Component Formulation (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-1B ™ 8.17 3 Andisil VS 250 ™ 1.34 4 Andisil VS65,000 ™ 23.74 5 Andisil XL-1B ™ 7.03 6 Andisil XL-11 ™ 8.36 7 AerosilR8200 ™ 14.71 8 Sepiplus 400 ™ 1.14 9 Water 21.76 10 Granhydrogel O ™6.40 11 Jeechem BUGL ™ 3.20 12 Sodium Chloride 0.32 13 Neolone PE ™ 0.3214 Iron Oxide Tint 0.01 MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 8 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 9 to 13 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 14 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 79-55g

Percent of Component Formulation No. Component (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-1B ™ 8.17 3 Andisil VS 250 ™ 1.29 4 Andisil MV 2,000 ™1.94 5 Andisil VS 20,000 ™ 22.91 6 Andisil XL-1B ™ 6.78 7 AndisilXL-11 ™ 8.07 8 Aerosil R8200 ™ 14.20 9 Sepiplus 400 ™ 1.14 10 Water21.76 11 Granhydrogel O ™ 6.40 12 Jeechem BUGL ™ 3.20 13 Sodium Chloride0.32 14 Neolone PE ™ 0.32 15 Iron Oxide Tint 0.01 MixtureProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 9 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 10 to 14 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 15 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 83-54

Percent of Component Formulation No. Component (%) 1 Andisil VS 10,000 ™27.58 2 Andisil VS 165,000 ™ 6.46 5 Andisil XL-11 ™ 13.50 6 AerosilR8200 ™ 17.50 7 Labrafac CC ™ 3.00 7 Sepiplus 400 ™ 1.44 8 Water 29.29 9Plantacare 818UP ™ 0.50 11 Sodium Chloride 0.36 12 Neolone PE ™ 0.36 13Iron Oxide Tint 0.01 MixtureProcedure:

Components 1 to 7 were added and mixed with a dual asymmetriccentrifugal mixer at 2500 RPM for 6 minutes until particulates are nolonger visible (Mixture A). In a separate vessel, components 8 to 12were mixed with a 4-blade, 40 mm propeller at 550 rpm until homogenous(Mixture B). Mixture B was added to Mixture A dropwise while mixing witha 4-blade 40 mm propeller at 400 rpm and the mixture was confirmed ashomogenous. Component 13 was added to the product of Mixture A andMixture B and mixed with 4-blade 40 mm propeller at 1000 rpm untilhomogenous.

Formulation 79-55h

Percent of Component Formulation No. Component (%) 1 Gransil EP-LS ™3.50 2 Andisil XL-1B ™ 8.15 3 Andisil VS 250 ™ 1.25 4 Andisil MV 2,000 ™1.85 5 Andisil VS 20,000 ™ 24.40 6 Andisil CE-4 ™ 1.85 7 Andisil XL-1B ™0.30 8 Andisil XL-11 ™ 10.80 9 Aerosil R8200 ™ 14.20 10 Sepiplus 400 ™1.14 11 Water 21.50 12 Granhydrogel O ™ 6.30 13 Jeechem BUGL ™ 3.15 14Sodium Chloride 0.30 15 Neolone PE ™ 0.30 16 Beaver UV/Fluorescent 1.00PigmentProcedure:

Components 1 and 2 were combined and homogenized until smooth at 20000RPM (Mixture A). Components 3 to 10 were added and mixed with a dualasymmetric centrifugal mixer at 2500 RPM for 6 minutes untilparticulates are no longer visible (Mixture B). Mixture A and Mixture Bwere combined and centrifuge mixed for 6 minutes at 2500 RPM (MixtureA+B). In a separate vessel, components 11 to 15 were mixed with a4-blade, 40 mm propeller at 550 rpm until homogenous (Mixture C).Mixture C was added to Mixture A+B dropwise while mixing with a 4-blade40 mm propeller at 400 rpm and the mixture was confirmed as homogenous.Component 15 was added to the product of Mixture A+B and Mixture C andmixed with 4-blade 40 mm propeller at 1000 rpm until homogenous.

Formulation 81-18

Component Percent of No. Component Formulation (%) 1 Dow 9011 Elastomer10.45 Blend 2 Dow 9045 Elastomer 10.45 Blend 3 Dow 245 Fluid 8.4 4Jeensilc CPS-312 2.09 5 PT-50175F 1.00 6 Water 30.33 7 Plantacare 818 UP0.55 8 Neolone PE 0.21 9 Propylene Glycol 20.87 10 Glycerin 4.16 11Jeechem BUGL 10.44 12 Sodium Chloride 1.05Procedure:

Components 1-5 were mixed in a glass beaker at 2000 rpm with 4-blade 40mm propeller for 2 minutes until mixture was homogeneous (Mixture A).Separately, components 6-12 were mixed until homogenous (Mixture B).Mixture B was added to Mixture A under strong agitation provided by a4-blade, 40 mm propeller at 2000 rpm until homogeneous. The finalformulation was further homogenized for 2 minutes.

Formulation 81-19

Component Percent of No. Component Formulation (%) 1 Dow 9011 Elastomer10.45 Blend 2 Dow 9045 Elastomer 10.45 Blend 3 Dow 245 Fluid 8.4 4Jeensilc CPS-312 2.09 5 PT-50175F 1.00 6 Water 29.83 7 Plantacare 818 UP0.55 8 Neolone PE 0.21 9 Propylene Glycol 20.87 10 Glycerin 4.16 11Jeechem BUGL 10.44 12 Sodium Chloride 1.05 13 Nylon 10-12 0.5Procedure:

Components 1-5 were mixed in a glass beaker at 2000 rpm with 4-blade 40mm propeller for 2 minutes until mixture was homogeneous (Mixture A).Separately, components 6-12 were mixed until homogenous (Mixture B).Mixture B was added to Mixture A under strong agitation provided by a4-blade, 40 mm propeller at 2000 rpm until homogeneous. Component 13 wasthen added and the resulting mixture was homogenized for 2 minutes.

Formulation 81-20

Component Percent of No. Component Formulation (%) 1 Dow 9011 Elastomer10.45 Blend 2 Dow 9045 Elastomer 10.45 Blend 3 Dow 245 Fluid 8.4 4Jeensilc CPS-312 2.09 5 PT-50175F 1.00 6 Water 29.33 7 Plantacare 818 UP0.55 8 Neolone PE 0.21 9 Propylene Glycol 20.87 10 Glycerin 4.16 11Jeechem BUGL 10.44 12 Sodium Chloride 1.05 13 Nylon 10-12 1.0Procedure:

Components 1-5 were nixed in a glass beaker at 2000 rpm with 4-blade 40mm propeller for 2 minutes until mixture was homogeneous (Mixture A).Separately, components 6-12 were mixed until homogenous (Mixture B).Mixture B was added to Mixture A under strong agitation provided by a4-blade, 40 mm propeller at 2000 rpm until homogeneous. Component 13 wasthen added and the resulting mixture was homogenized for 2 minutes.

Formulation 81-21

Component Percent of No. Component Formulation (%) 1 Dow 9011 Elastomer10.45 Blend 2 Dow 9045 Elastomer 10.45 Blend 3 Dow 245 Fluid 8.4 4Jeensilc CPS-312 2.09 5 PT-50175F 1.00 6 Water 27.33 7 Plantacare 818 UP0.55 8 Neolone PE 0.21 9 Propylene Glycol 20.87 10 Glycerin 4.16 11Jeechem BUGL 10.44 12 Sodium Chloride 1.05 13 Nylon 10-12 3.0Procedure:

Components 1-5 were mixed in a glass beaker at 2000 rpm with 4-blade 40mm propeller for 2 minutes until mixture was homogeneous (Mixture. A).Separately, components 6-12 were mixed until homogenous (Mixture B).Mixture B was added to Mixture A under strong agitation provided by a4-blade, 40 mm propeller at 2000 rpm until homogeneous. Component 13 wasthen added and the resulting mixture was homogenized for 2 minutes.

Formulation 79-74

Percent of Component Formulation No. Component (%) 1 Andisil VS 10,000 ™27.58 2 Andisil VS 165,000 ™ 6.46 5 Andisil XL-11 ™ 13.50 6 AerosilR8200 ™ 17.50 7 Schercemol ™ 318 Ester 3.00 7 Sepiplus 400 ™ 1.44 8Water 29.29 9 Plantacare 818UP ™ 0.50 11 Sodium Chloride 0.36 12 NeolonePE ™ 0.36 13 Iron Oxide Tint Mixture 0.01Procedure:

Components 1 to 7 were added and mixed with a dual asymmetriccentrifugal mixer at 2500 RPM for 6 minutes until particulates are nolonger visible (Mixture A). In a separate vessel, components 8 to 12were mixed with a 4-blade, 40 mm propeller at 550 rpm until homogenous(Mixture B). Mixture B was added to Mixture A dropwise while mixing witha 4-blade 40 mm propeller at 400 rpm and the mixture was confirmed ashomogenous. Component 13 was added to the product of Mixture A andMixture B and mixed with 4-blade 40 mm propeller at 1000 rpm untilhomogenous.

Pigment Dispersion Formulation 80-23

Component Percent of No. Component Formulation (%) 1 Dow 9011 Elastomer10 Blend 2 Dow 9045 Elastomer 10 Blend 3 Dow 245 Fluid 10 4 Water 27 5Plantacare 818 UP 0.5 6 Neolone PE 0.5 7 Propylene Glycol 20 8 Glycerin4 9 Jeechem BUGL 10 10 Sodium Chloride 1 11 Nylon 4.5 12 Tint 2.5Procedure:

Components 1-3 were mixed in a glass beaker at 2000 rpm with 4-blade 40mm propeller for 2 minutes until homogenous (Mixture A). Separately,components 5-10 were mixed until homogenous (Mixture B). Mixture wasadded B to Mixture A under strong agitation, provided by a 4-blade, 40mm propeller at 2000 rpm until homogeneous. Components 11 and 12 werethen added and mix at 200 rpm and until homogeneous. The final mixturewas then homogenized for 2 minutes.

Formulation 79-88

Percent of Component Formulation No. Component (%) 1 Andisil VS 10,000 ™27.59 2 Andisil VS 165,000 ™ 6.46 3 Andisil XL-11 ™ 13.50 4 AerosilR8200 ™ 17.50 5 Labrafac CC ™ 3.00 6 Sepiplus 400 ™ 1.44 7 Water 29.29 8Plantacare 818UP ™ 0.50 9 Sodium Chloride 0.36 10 Neolone PE ™ 0.36Procedure:

Components 1 to 4 were combined and mixed with KitchenAid mixer for 5hours. Subsequently the mixture was vacuumed overnight. Components 5 and6 were then added and the mixture was homogenized in a dual asymmetriccentrifugal mixer at 2500 RPM. In a separate vessel, components 7 to 10were mixed with a 4-blade, 40 mm propeller at 550 rpm until homogenous(Mixture B). Mixture B was added to Mixture A dropwise while mixing witha 4-blade 40 mm propeller at 500 rpm and the mixture was confirmed ashomogenous.

Formulation 79-88-3A

Percent of Component Formulation No. Component (%) 1 Andisil VS 10,000 ™27.59 2 Andisil VS 165,000 ™ 6.46 3 Andisil XL-11 ™ 13.50 4 AerosilR8200 ™ 17.50 5 Labrafac CC ™ 3.00 6 Simulgel EG ™ 1.44 7 Water 29.29 8Plantacare 818UP ™ 0.50 9 Sodium Chloride 0.36 10 Neolone PE ™ 0.36Procedure:

Components 1 to 4 were combined and mixed with KitchenAid mixer for 5hours. Subsequently the mixture was vacuumed overnight. Components 5 and6 were then added and the mixture was homogenized in a dual asymmetriccentrifugal mixer at 2500 RPM. In a separate vessel, components 7 to 10were mixed with a 4-blade, 40 mm propeller at 550 rpm until homogenous(Mixture B). Mixture B was added to Mixture A dropwise while mixing witha 4-blade 40 mm propeller at 500 rpm and the mixture was confirmed ashomogenous.

Formulation 79-74-RD

Percent of Component Formulation No. Component (%) 1 Andisil VS 500 ™0.52 2 Andisil MV 2000 ™ 0.80 3 Andisil VS 65,000 ™ 13.04 4 AndisilXL-1B ™ 16.84 5 Aerosil R8200 ™ 8.80 6 Water 50.00 7 Veegum Pro 4.00 8Solagum AX 1.00 9 Dow Corning 5329 5.00Procedure:

Components 1 to 5 were combined and mixed under vacuum (Mixture A). In aseparate vessel, components 6 to 7 were mixed with a 4-blade, 40 mmpropeller at 550 rpm until the mixture was homogenous and theparticulates were fully wetted (Mixture B). Component 8 was added toMixture B and mixed in with a 4-blade 40 mm propeller at 500 rpm untilthe mixture thickened and became homogenous. Component 9 was added toMixture B and mixed in with a 4-blade 40 mm propeller at 500 rpm for 10minutes. Mixture B was added slowly to Mixture B under continuous mixingat 500 rpm. The product was homogenized for 5 minutes at 10,000 rpm.

Formulation 79-90-B

Percent of Component Formulation No. Component (%) 1 Andisil VS 500 ™0.68 2 Andisil MV 2000 ™ 1.04 3 Andisil VS 65,000 ™ 16.95 4 AndisilXL-1B ™ 21.89 5 Aerosil R8200 ™ 11.44 6 Water 40.00 7 Veegum Pro 4.00 8Solagum AX 1.00 9 Dow Corning 5329 3.00Procedure:

Components 1 to 5 were combined and mixed under vacuum (Mixture). In aseparate vessel, components 6 to 7 were mixed with a 4-blade, 40 mmpropeller at 550 rpm until the mixture was homogenous and theparticulates were fully wetted (Mixture B). Component 8 was added toMixture B and mixed in with a 4-blade 40 mm propeller at 500 rpm untilthe mixture thickened and became homogenous. Component 9 was added toMixture B and mixed in with a 4-blade 40 mm propeller at 500 rpm for 10minutes. Mixture A was added slowly to Mixture B under continuous mixingat 500 rpm. The product was homogenized for 5 minutes at 10,000 rpm.

Formulation 88-70

Component Percent of No. Component Formulation (%) 1 Andisil VS10,00028.7% 2 Andisil 6.7% VS165,000 3 Andisil XL-11 14.0% 5 Aerosil R820018.2% 6 KF6013 2.1% 7 TMF 1.5 2.3% 8 USG 102 2.3% 9 DI water 22.3% 10Glycerin 1.1% 11 Jeen BUGL 1.2% 12 Jeecide Cap-5 1.0%Procedure:

Components 1-8 (part) and components 9-11 (part B). Part B wasintroduced to part A while mixing part A with a flat propeller blade at500 RPM. The resulting solution was mixed until a uniform emulsionformed. Component 12 was subsequently added to the emulsion.

Formulation 88-72

Component Percent of No. Component Formulation (%) 1 Andisil VS10,00028.60% 2 Andisil 6.69% VS165,000 3 Andisil XL-11 13.99% 5 Aerosil R820018.16% 6 KF6013 2.08% 7 TMF 1.5 2.25% 8 USG 102 2.35% 9 Pink tint mix0.02% 10 DI water 22.25% 11 Glycerin 1.16% 12 Jeen BUGL 1.24% 13 VeegumUltra 0.11% Granules 14 Kaolin USP 0.10% BC2747 15 Jeecide Cap-5 1.00%Procedure:

Components 1-9 (Phase A) were mixed separately from components 10-14(Phase B). Phase B was added to Phase A while mixing at 500 RPM using a4 paddle mixing blade, followed by homogenization using a Silversonhomogenizer for 1 hour at 3000 to 5000 RPM. Subsequently, component 15was added using mixing blade at 200 rpm.

Formulation 88-75-2

Percent of Component Formulation No. Component (%) 1 Andisil VS10,00021.39% 2 Andisil 5.00% VS165,000 3 Andisil XL-11 10.47% 4 Aerosil R820013.58% 5 RM2051 1.95% 6 DC 556 3.12% 7 FZ3196 3.11% 8 Squalane 1.85% 9USG 102 6.90% 10 Jeechem BUGL 1.85% 11 DI water 29.03% 12 PolyglycolP425 1.22% 13 Jeecide Cap-5 0.52%Procedure:

Components 1-4 (Phase A) were mixed. Separately, components 5-9 werealso mixed (Phase B) until a uniform dispersion was formed. Components10-12 (Phase C) were also mixed separately. Phase C was slowlyintroduced into Phase B, while mixing at 700 RPM with 4 blade propellerrod to create a uniform emulsion (Phase B). Phase D was slowlyintroduced into Phase A at 700 RPM until uniform, and the resultingformulation was mixed for 5 minutes. Component 13 was added and mixedfor 2 minutes.

Formulation 88-75-3

Percent of Component Formulation No. Component (%) 1 Andisil VS10,00018.64% 2 Andisil 4.36% VS165,000 3 Andisil XL-11 9.12% 4 Aerosil R820011.84% 5 RM2051 2.21% 6 DC 556 3.53% 7 FZ3196 3.52% 8 Squalane 2.10% 9USG 102 7.81% 10 Jeechem BUGL 2.10% 11 DI water 32.85% 12 PolyglycolP425 1.38% 13 Jeecide Cap-5 0.54%Procedure:

Components 1-4 (Phase A) were mixed. Components 5-9 (Phase B) were mixedseparately from Phase A until a uniform dispersion was formed.Components 10-12 (Phase C) were also mixed separately from Phase A andPhase B. Phase C was slowly introduced into Phase B, while mixing at 700RPM with 4 blade propeller rod to create a uniform emulsion (Phase D).Phase D was Slowly introduced to Phase A at 700 RPM until uniform, andmixed for 5 minutes. Component 13 was then introduced to the resultingformulation and mixed for 2 minutes, followed by homogenization at 5000RPM for 15 minutes.

Formulation 88-80

Percent of Component Formulation No. Component (%) 1 Andisil VS10,00012.72%  2 Andisil 2.98% VS165,000 3 Andisil XL-11 6.23% 4 Aerosil R82008.08% 5 RM2051 2.79% 6 DC 556 4.45% 7 FZ3196 4.44% 8 Squalane 2.64% 9USG 102 9.85% 10 Jeechem BUGL 2.64% 11 DI water 41.44%  12 PolyglycolP425 1.74% 13 Jeecide Cap-5 0.005% Procedure:

Components 1-4 (Phase A) were mixed. Components 5-9 (Phase B) were mixedseparately from Phase A until a uniform dispersion was formed.Components 10-12 (Phase C) were also mixed separately from Phase A andPhase B. Phase C was slowly introduced into Phase B, while mixing at 700RPM with 4 blade propeller rod to create a uniform emulsion (Phase D).Component 13 was added to Phase D and mixed for 2 minutes. The resultingemulsion was lowly introduced into Phase A at 700 RPM until uniform, andmixed for 5 minutes, followed by homogenization at 9000 RPM for 7minutes.

Formulation 88-85-1

Percent of Component Formulation No. Component (%) 1 RM 2051 3.28% 2 FZ3196 4.92% 3 USG 102 12.11% 4 water 48.83% 5 Jeecide CAP-5 0.87% 6Andisil VS10,000 12.72% 7 Andisil 2.98% VS165,000 8 Andisil XL-11 6.23%9 Aerosil R8200 8.08%Procedure:

Components 1-3 (Phase A) were mixed. Component 4 was added while mixingPhase A, until a white emulsion formed. Components 6-9 (Phase B) weremixed and Phase B was subsequently added to the emulsion and mixed for 5minutes at 1300 RPM. The resulting formulation was homogenized(Silverson) for 5 minutes and component 5 was added, followed by mixingfor 2 minutes at 700 RPM with a propeller blade.

Formulation 88-85-2

Percent of Component Formulation No. Component (%) 1 RM 2051 2.62% 2 FZ3196 3.93% 3 USG 102 9.68% 4 water 39.03%  5 Jeecide CAP-5 0.78% 6Andisil VS10,000 18.6% 7 Andisil  4.4% VS165,000 8 Andisil XL-11  9.1% 9Aerosil R8200 11.8%Procedure:

Components 1-3 (Phase A) were mixed. Component 4 was added while mixingphase A until a white emulsion formed. Components, 6-9 (Phase B) weremixed separately and subsequently added to the emulsion while mixing at1300 RPM for 5 minutes. The mixture was homogenized (Silverson) for 5minutes. Component 5 was added and the resulting formulation was mixedfor 2 minutes at 700 RPM with a propeller blade.

Formulation 88-83-V2

Percent of Component Formulation No. Component (%) 1 RM 2051 3.3% 2 FZ3196 3.3% 3 DC 2-1184 fluid 10.0% 4 USG 102 3.3% 5 water 46.3% 6 JeecideCAP-5 0.3% 7 Andisil VS10,000 14.1% 8 Andisil 3.3% VS165,000 9 AndisilXL-11 6.9% 10 Aerosil R8200 9.0%Procedure:

Components 1-4 were mixed (Phase A), followed by addition of component5, until a white emulsion formed. Component 6 was added to the emulsionand mixed for 5 minutes (emulsion base). Components 7-10 (Phase B) weremixed separately and added to the emulsion base at 1300 RPM, followed bymixing for 5 minutes and homogenization (Silverson) for 10 minutes.

Formulation 88-83-V3

Percent of Component Formulation No. Component (%) 1 RM 2051 3.3% 2 DC2-1184 fluid 13.3% 3 water 49.7% 4 Jeecide CAP-5 0.3% 5 Andisil VS10,00014.1% 6 Andisil VS165,000 3.3% 7 Andisil XL-11 6.9% 8 Aerosil R8200 9.0%Procedure:

Components 1 and 2 were mixed (Phase A), followed by addition ofcomponent 3, until a white emulsion formed. Component 4 was added to theemulsion and mixed for 5 minutes (emulsion base). Components 5-8 (PhaseB) were mixed separately and added to the emulsion base at 1300 RPM,followed by mixing for 5 minutes and homogenization (Silverson) for 10minutes.

Formulation 83-54

Reactive Constituent and Reinforcing Constituent Composition (Vinyl,Hydride, Fumed Silica)

weight ranges Tradename Description percent lower upper Andisil VS10,0000.05 mmol/g vinyl, 10,000 42.40% 30 50 cSt Andisil VS165,000 0.015mmol/g vinyl, 9.92% 5 15 165,000 cSt Andisil XL-11 4.35 mmol/g, 45 cSt20.75% 10 30 Aerosil R8200 Silica Silylate 26.93% 20 34 total 100.00%Reactive Reinforcing Component RM 2051 Thickening Sodium Polyacrylate(and) 3.63% 3.00% 5.00% Agent Dimethicone (and) Cyclopentasiloxane (and)Trideceth-6 (and) PEG/PPG-18/18 Dimethicone Gransurf 90 CetylPEG/PPG-10/1 0.50% 0.20% 2.00% Dimethicone PMX-1184 dimethicone andtrisiloxane 13.63% 10.00% 40.00% Water N/A 46.00% 20.00% 60.00%Vitamin-C complex Ascorbic Acid 0.08% 0.05% 0.50% Jeecide CAP-5Phenoxyethanol, Caprylyl 0.33% 1.00% Glycol, Potassium Sorbate, Aqua,Hexylene Glycol Tween 20 Polysorbate 20 0.33% 5.00% Vitamin-A complexVitamin A Palmitate 1.7 MIU/g 0.40% 5.00% Vitamin-E complex Vitamin EAcetate 0.10% 5.00% Reactive constituent N/A 35.00% 30.00% 60.00% andReinforcing constituent composition (Vinyl, hydride, fumed silica) fromabove total 100.00%Procedure:

Formulation 83-54 was prepared by a procedure similar to 88-83-V3.

Andisil VS10,000, Andisil VS165,000, Andisil XL-11 were obtained fromAnderson and Associates, Aerosil 88200 was obtained from Evonik, and thefour components were mixed by Crisil. RM 2051 Thickening Agent andPMX-1184 were obtained from Dow. Gransurf 90 was obtained from Grant.Vitamin-C complex and Vitamin A complex were obtained from DSM. JeecideCAP-5 was obtained from Jeen. Tween 20 was obtained from Croda.Vitamin-E complex was obtained from TRI-K.

The cross-linking component second step includes formulations 60-148-99,60-144-San 86-114, and 86-141c shown below.

Formulation 60-148-99

Component Percent of No. Component Formulation (%) 1 Water 28.60 2Plantacare 818UP 0.49 3 Propylene Glycol 19.72 4 Glycerin 3.94 5 JeechemBUGL 9.86 6 Sodium Chloride 0.99 7 Dow Elastomer 9.86 Blend 9011 8 DowElastomer 9.86 Blend 9041 9 Dow 245 Fluid 7.89 10 Jeensilc CPS-312 1.9711 Nylon 10-12 4.64 12 Chronosphere 0.18 Optical Brite 13 Platinumdivinyl 1.00 complex PC 075.3Procedure:

Components 1-6 were combined and mixed at 750 RPM fix two minutes with a4-blade 40 mm propeller until homogenous to create an aqueous phase. Ina separate container components 7-10 were mixed at 750 RPM for twominutes with a 4-blade 40 mm propeller until homogenous to create aSilicon Mixture A. To the aqueous phase, components 11 and 12 were addedand mixed at 750 RPM with a 4-blade 40 mm propeller. The mixing speedwas increased to 1000 RPM and the mixture was mixed until homogenous andthickened. Component 13 was added and stirred at 1000 RPM for 1 minute,then homogenized at 25,000 RPM for 5 minutes.

Formulation 60-144-San

Component Percent of No. Component Formulation (%) 1 Water 67.47 2Carbopol Ultrez 1.01 21 3 Denatured Ethanol 29.35 190 Proof 4 Glycerin2.02 5 2% Sodium 0.20 Hydroxide 6 Platinum divinyl 1.99 complex 3% PC075.3Procedure:

Components 1 and 2 were gently blended with a 4-blade 40 mm propellerblade at 250 RPM until the Carbopol was completely wetted and themixture was free of white particulates. Components 3 and 4 were addedunder moderate agitation provided by a 4-blade 40 mm propeller at 500RPM. Component 5 was added dropwise under moderate agitation provided bya 4-blade 40 mm propeller at 550 RPM until the mixture was homogenousand thickened. Component 6 was added under moderate agitation providedby a 4-blade 40 mm propeller at 550 RPM, followed by mixing at 1000 RPMfor 5 minutes until the mixture was homogeneous.

Formulation 86-114 and 86-141c

weight Tradename Description percent Supplier lower upper PlatinumKarstedt's catalyst in 1.00% Umicore 0.50% 2.50% Divinyl stabilizingvinyl- Complex 2% dimethicone PT-50175F (CAS# 68478-92-2, 2627-95-4,68083-19-2) 1.00% total Crosslinking 86-114 Component #1 lower upper Dow9011 Cyclopentasiloxane 10.00% Dow 5.00% 20.00% Elastomer (and) PEG-12Corning Blend Dimethicone Crosspolymer Dow 9045 Cyclopentasiloxane and10.00% Dow 5.00% 20.00% Elastomer Dimethicone Corning Blend CrosspolymerPMX-0245 Cyclopentasiloxane 10.00% Dow 5.00% 25.00% Corning Water 28.50%NA — 90.00% Sodium Sodium Chloride 1.00% Spectrum — 5.00% ChloridePlantacare Coco-Glucoside 0.50% Cognis — 4.00% 818 UP Tween 20Polysorbate 20 0.00% Cognis — 2.00% Propylene Propylene Glycol 20.00%Ruger — 40.00% Glycol Chemical Co Lipo PEG-4 0.00% Lipo — 40.00%Polyglycol ® Chemicals 200 Inc Glycerin Glycerin 4.00% Ruger — 10.00%Chemical Co Jeechem 1,3-Butylene Glycol 10.00% Jeen — 50.00% BUGL Nylon10-12 Nylon 12 and Isopropyl 4.50% KOBO — 15.00% Titabium TriisostearateJeecide CAP-5 Phenoxyethanol, 0.50% Jeen — 2.00% Caprylyl Glycol,Potassium Sorbate, Aqua, Hexylene Glycol PT-50175F Platinum 1.00%Umicore 0.50% 2.50% Divinyldisiloxane total 100.00% total Crosslinking86-141c Component #2 lower upper KSG-240 Dimethicone/PEG- 10.00% ShinEtsu 3.00% 20.00% 10/15 Crosspolymer DC 9045 Cyclopentasiloxane and7.50% Dow 25.00% Dimethicone Corning Crosspolymer KF-995Cyclopentasiloxane 11.50% Shin Etsu 25.00% KF-6028 PEG-9 1.00% Shin Etsu4.00% Polydimethylsiloxyethyl Dimethicone Water 28.25% NA 90.00% SodiumSodium Chloride 1.00% Spectrum 5.00% Chloride Plantacare Coco-Glucoside0.50% Cognis 4.00% 818 UP Tween 20 Polysorbate 20 0.00% Cognis 2.00%Propylene Propylene Glycol 20.00% Ruger 40.00% Glycol Chemical Co LipoPEG-4 0.00% Lipo — 40.00% Polyglycol ® Chemicals 200 Inc GlycerinGlycerin 4.00% Ruger 10.00% Chemical Co Jeechem 1,3-Butylene Glycol10.00% Jeen 50.00% BUGL Nylon 10-12 Nylon 12 and Isopropyl 4.50% KOBO15.00% Titabium Triisostearate Jeecide CAP-5 Phenoxyethanol, 0.50% Jeen2.00% Caprylyl Glycol, Potassium Sorbate, Aqua, Hexylene GlycolPT-50175F Platinum 1.25% Umicore 2.50% Divinyldisiloxane 100.00% totalProcedure for 86-114:

Components 1-3 were combined and mixed at 750 RPM for two minutes withuntil homogenous to create an silicone phase. In a separate containercomponents 4-11 and 13 were mixed at 750 RPM for 15 minutes with a untilhomogenous to create a water phase. The water phase was added slowly tothe silicone phase and mixed at 750 RPM. The mixing speed was increasedto 2000 RPM and the mixture was mixed until homogenous and thickened.Component 12 was added and stirred at 1000 RPM for 5 minutes. Component14 was added and stirred at 1000 RPM for 5 minutes.

Procedure for 86-141c:

Components 1-4 were combined and mixed at 750 RPM for two minutes withuntil homogenous to create an silicone phase. In a separate containercomponents 5-12 and 14 were mixed at 750 RPM for 15 minutes with a untilhomogenous to create a water phase. The water phase was added slowly tothe silicone phase and mixed at 750 RPM. The mixing speed was increasedto 2000 RPM and the mixture was mixed until homogenous and thickened.Component 13 was added and stirred at 1000 RPM for 5 minutes. Component15 was added and stirred at 1000 RPM for 5 minutes.

Example 6 Development of Cleanser to Remove Therapeutic Compositions

It was found that commercially available cleansers were not effective atremoving the film formed upon application of the therapeuticcompositions of the invention. To evaluate the performance of thecleansers, the film was applied to facial skin of volunteers. Followingsix to eight hours, the cleanser was rubbed onto the film and left onthe film for 30 seconds. The subject was then instructed to remove thefilm with a towelette of a given surface roughness by gentle wiping theswollen film from the skin. The following commercially availableproducts were tested:

Philosophy Purity Made Simple

Shiseido Benefiance Creamy Cleansing foam

Noxema

Estee Lauder Perfectly Clean Splash Away Foaming Cleanser

Makeup forever sens'eyes

Loreal go 360clean deep

Clinique naturally gentle eye makeup remover

Olay Total Effects 7 in 1 antiaging cleanser

Olay dual action cleanser and pore scrub

Garnier Skin Renew

Lancome Bi-Facil double action make-up remover

Neutrogena deep clean invigorating foaming scrub

Olay regenerist daily regenerating cleanser

CVS pharmacy deep cleansing makeup remover

Neutrogena Ageless essentials Continuous Hydration Cream Cleanser

CVS cleansing and makeup remover

Yes to cucumbers natural glow facial towelettes

As none of the aforementioned products were effective at removing thefilm, a cleanser was prepared to disrupt the mechanical integrity of thefilm and to facilitate the delivery of the cleanser components into thefilm. Without being hound by theory, the removal mechanism can bedescribed in four steps with key formula components for each stepindicated in parentheses:

-   -   1. Film wetting (Silsoft 034, Silsoft ETS, 5CS dimethicone)    -   2. Penetration of formula components (siloxane emulsifiers,        siloxane phase, glycols, Cremaphor EL)    -   3. Film swelling (Silsoft 034, Silsoft ETS, Isododecane, 5CS        dimethicone)    -   4. Film release from skin (glycols, water)

Silsoft 034, Silsoft ETS, 5CS dimethicone readily wet the surface of thefilm. The siloxane emulsifiers or the Cremaphor EL incorporate theaqueous phase into the siloxane phase, and may facilitate delivery ofthe film swelling components into the film. Silsoft 034, isododecane,and Silsoft ETS contribute to swelling the film and mechanicaldisruption. This enables penetration of the aqueous phase, hydration ofthe skin and reduction of the film's adhesion to the skin.

Tables 15-17, below, provide compositions that were effective inremoving the film:

TABLE 15 siloxane phase w/w gm Silsoft 034 (caprylyl methicone) 9.7% 5Isododecane 19.4% 10 Silsoft ETS (ethyl trisiloxane) 19.4% 10 AerogelVM2270 1.5% 0.763 siloxane emulsifiers Shin Etsu KSG 820 3.9% 2 ShinEtsu KF 6038 3.9% 2 aqueous phase propylene glycol 4.9% 2.5 butylenediglycol 4.9% 2.5 glycerol 1.9% 1 MPDiol 7.8% 4 DI water 19.4% 10neolone PE 0.5% 0.27 chronosphere optical brite 0.6% 0.3 granpowdernylon 2.1% 1.1

TABLE 16 Component Percent of No. Component Formulation (%) 1 Glycerin3.00% 2 water 43.98% 3 dowanol DPM 6.00% 5 cremaphor EL 6.00% 6 silsoftETS 30.00% 7 DM5 CS 10.00% 8 prestige pearlescent 0.02% beige 9 Jeecidecap 5 1.00%

TABLE 17 Percent of Component Formulation No. Component (%) 1 Glycerin3.11% 2 water 46.23% 3 dowanol DPM 6.20% 4 cremaphor EL 6.22% 5 silsoftETS 12.43% 6 DC 200 Fluid 15.49% (1 cSt) 7 DM5 CS 9.30% 8 Xironacaribbean 0.02% blue 9 Jeecide cap 5 1.00%Procedure:

Components 1-4 and 9 were mixed until a clear dispersion formed (PhaseA). Compounds 5-8 were mixed separately until a uniform solidsdispersion was formed. Phase A was subsequently added to Phase B andMixed.

Example 7 Viscosity Measurements

The viscosity of a fluid can be measured by many methods known to one ofskill in the art. Specifically, “The rheology handbook: for users ofrotational and oscillatory rheometers By Thomas G. Mezger” or ASTMstandards such as ASTM D3835-08, ASTM D2857-95, ASTM D2196-10, and ASTMD2983-09 instruct one of skill in the an on how to measure the viscosityof a fluid. Illustrative methods also include the following methods:

Method A

I. Overview

This protocol determines the viscosity (cP) on a Brookfield Viscometer.This protocol can be performed on a wide variety of formulationsincluding but not limited to immediate effects treatment, and perfector.

II. Background

The viscosity of formulation is critical to its performance and itsaesthetics. Furthermore a change in viscosity with time or exposure to astress condition is an important indicator of formulation instability.As such, it is important to be able to reproducibly and accuratelyevaluate formulation viscosity. The following protocol can be used todetermine the viscosity at single shear rate of a formulation whoseviscosity is between 50 and 300 Pas.

III. Materials

-   -   A full 2 oz to 8 oz jar containing formulation of interest    -   Brookfield Pro EXTRA Viscometer and RV-6 spindle.    -   Test requires ˜5 minutes per sample

IV. Analytical Precautions

-   -   Clean the viscometer geometry prior to use    -   insert the geometry to the appropriate depth in the center of        the sample container    -   Insure the container is stationary during the test

V. Protocol

5.1 Preparing Equipment:

-   -   1. Turn on the Brookfield DV-II+ Pro EXTRA Viscometer by        pressing a switch in the back of the instrument. Select        “External Mode” by pressing the up arrow on the instrument        control panel.    -   2. Start the Rheocalc software, a shortcut to which can be found        on the desktop    -   3. Zero the viscometer by clicking the lightning symbol on the        dashboard tab (Instrument geometry should NOT be installed)    -   4. Find RV-6 test geometry and clean with 50%/50% IPA/Mineral        Spirits mixture, then wipe dry    -   5. Insert RV-6 geometry by pulling the instrument geometry        holder sleeve    -   6. Pick the test method by clicking Test tab, and opening        Hold0.5-RV6-081511.RCP method.

5.2 Preparing Sample:

1. No special sample preparation is required other than doing a visualinspection to ensure the sample appears uniform.

5.3 Perform Viscosity Measurement:

-   -   1. Insert the geometry into the 2 to 8 oz of sample under.        -   i. Insure that the geometry is inserted to the correct            measuring height as indicated by thin section in the rod of            the geometry        -   ii. Insure that the geometry is centered in the jar    -   2. Adjust the stand so as to keep the sample and the geometry in        the appropriate relative position.    -   3. Click the small play button in the test tab to start the test    -   4. Name the data file appropriately and save the file to the        appropriate location    -   5. Allow the test to run to completion, then save your data for        later analysis    -   6. To test another sample:        -   i. Slide the sample stand out and remove the sample from the            instrument        -   ii. Remove the geometry from the instrument and gently wipe            down all surfaces with 50% IPA, 50% Mineral Spirit mixture.            Dry with a lint free wipe.            -   iii. Replace the geometry, return to test tab and start                next test    -   7. After finishing with the last test sample, clean geometry        with 50% IPA, 50% Mineral Spirit mixture, then wipe dry and        place back in geometry box.

VI. Data Analysis

-   -   1. Open datafile (*.DB) and click the export button to obtain an        excel file containing the data.    -   2. Locate the        ViscometerPerfectorTemplate_JL-081511-v1-beta1.xlsx Excel        template for data analysis    -   3. Paste the data into the first sheet    -   4. Record the average viscosity and the standard deviation    -   5. Save the template as an electronic record with a new name        that references the analyzed sample.    -   1. Repeat analysis for each data set.        Method B

I. Overview

This protocol determines the viscosity (Pas) at 0.5 l/s, Shear Thinningfactor (Pa*s^2), and the strain rate of instability. This protocol canbe performed on a wide variety of formulations including but not limitedto immediate effects treatment, and perfector, along with any other“cream” or “lotion”

II. Background

The viscosity of formulas and its change has been correlated tostability of formulations. As such, it is important to be able toreproducibly and accurately evaluate their viscosity properties to beused as a predictive tool for stability of Immediate Effects activeprototypes. The following protocol can be used to determine theviscosity, shear thinning factor, and strain rate of instability.

III. Materials

-   -   >1 g Formulation of Interest    -   Bohlin CVO100 Rheometer mounted with 20 mm Parallel plate        geometry    -   Test requires ˜12 minutes per sample

IV. Analytical Precautions

-   -   Clean sides of the geometry are critical for accurate test        results    -   Any deviations must be noted

V. Protocol

5.1 Preparing Equipment:

-   -   8. Set up the Bohlin Rheometer        -   a. Turn on the instrument        -   b. Turn on the temperature controller        -   c. Start the Bohlin software        -   d. Load the viscosity stability test template        -   e. Make sure both the geometry and plate are clean    -   9. Install the geometry        -   a. Zero the instrument and you are now ready to being            testing.    -   10. For testing of multiple samples simply raise and clean the        geometry first with a dry wipe, then with a 50%/50% IPA/Mineral        Spirits mixture, then again with a dry wipe.

5.2 Preparing Sample:

-   -   1. No special sample preparation is required other than doing a        visual inspection to ensure the sample appears uniform.

VI. Perform the Viscosity Test

-   -   7. Place ˜1 g of mixed material onto the bottom plate in a mound        centered below the geometry    -   8. Lower the geometry to the correct gap (250 um)    -   9. Clean the excess material from the sides of the geometry        using the flat end of a spatula    -   10. Allow the test to run to completion, then save your data for        later analysis    -   11. To continue onto the next test, raise the geometry and        remove the sample from the instrument. Gently wipe down all        surfaces with 50% ipa/50% mineral spirits mixture. Dry with a        lint free wipe.    -   12. You are now ready to commence the next cure test

VII. Data Analysis:

-   -   2. Locate the following Excel Template for the data analysis        ViscosityStabilityTemplate061411-v2    -   3. Paste the raw instrument data from the appropriate Bohlin        Viscometry Data File file into A:2 of sheet 1 (near the left        corner) of the excel document    -   4. Paste the sample name into A:1 of sheet 1 of the excel        document    -   5. Record the calculated “Viscosity (Pas) at 0.5 l/s” as        viscosity    -   6. Record the calculated “Shear Thinning factor (Pa*s^2)” as the        shear thinning factor    -   7. Record the calculated “Strain Rate of instability” as the        Strain Stability (Scale is out of 100)    -   8. Save the completed template as an electronic record with an        appropriate file name    -   9. Repeat steps 2 to 7 for remaining raw data

Example 8 Use of Compositions to Treat Headaches and Wounds

A. Headache Use:

The reactive reinforcing component formulation of the invention can beused to treat tension headaches. A representative formulation isprovided below.

Application.

To treat the headache, apply an even layer of the formulation,approximately 0.05 g per square inch on to the forehead, covering thespace between the hair line and the brows. Immediately afterwards, applythe crosslinking component on top, covering and extending past the areacovered by the reactive reinforcing component. The crosslinkingcomponent can be applied at a concentration of approximate 0.1 g persquare inch. Allow approximately 15 minutes for the applied formulationsto set and form a visually pleasing film.

Effect of Film on Treatment Area.

The resulting film provides mechanical support that relieves the load onface and neck muscles that are responsible for tension headacheseffectively relieving the headache. Within minutes to hours the musclesrelax in response to the reduced load and the headache is reduced. Thefilm should be worn for as long as headache relief is desired. Toremove, a removal solution can be used. The product can be reapplieddaily or as often as desired by repeating the procedure above.

Additionally, the support offered by the set formulations produces abrow lift. The brow lift improves the appearance of the eye anddiminishes the eye obstruction by the brow (eye lid drooping) in somecases improving comfort and vision. The set formulations arecosmetically pleasing, visual unobtrusive, and provide a non-invasivesolution to a tension headache without systemic chemical side effectsassociated with oral or injection medication.

B. Wound Use:

The reactive reinforcing component formulation of the invention can beused to treat a skin wound. A representative formulation for this use isprovided below.

Application.

To treat the wound, apply an even layer of the formulation,approximately 0.05 g per square inch on top of and surrounding the woundthat has been blotted dry. Immediately afterwards, apply thecrosslinking component on top of the formulation, covering and extendingpast the area covered by the reactive reinforcing component. Thecrosslinking component can be applied at a concentration of approximate0.1 g per square inch. Allow approximately 15 minutes for the appliedformulations to set and form a visually pleasing film. The film shouldbe worn for as long as the wound persists. To remove, a removal solutioncan be used. The product can be reapplied daily or as often as desiredby repeating the procedure above.

Effect of Film on Treatment Area.

Within minutes to hours the skin relaxes in response to the reduced loadand the wound healing time is reduced. The resulting film providesmechanical support that relieves the load on wound, reducing scarformation. Furthermore the film provides an occlusive protectivecovering for the wound that protects the wound from physical andchemical attack while it is healing. The film has hydration andbiocompatibility properties that improve wound recovery. Furthermore thefilm aids the controlled sustained delivery of imbedded wound healingactives directly to the wound site. The film is comfortable andaesthetically unobtrusive aiding, thereby increasing subject compliance.

Formulation 79-110-1

Reactive Constituent and Reinforcing Constituent Composition (Vinyl,Hydride, Fumed Silica)

weight ranges Tradename Description percent lower upper Andisil VS10,0000.05 mmol/g vinyl, 10,000 cSt 37.7% 30 50 Andisil VS165,000 0.015 mmol/gvinyl, 8.8% 5 15 165,000 cSt Andisil XL-11 4.35 mmol/g, 45 cSt 18.5% 1030 Aerosil R8200 Silica Silylate 35.0% 20 50 total 100.00% ReactiveReinforcing Component RM 2051 Thickening Sodium Polyacrylate (and) 3.63%3.00% 5.00% Agent Dimethicone (and) Cyclopentasiloxane (and) Trideceth-6(and) PEG/PPG-18/18 Dimethicone Dow 9011 Elastomer Cyclopentasiloxane(and) 20.00% Blend PEG-12 Dimethicone Crosspolymer PMX-1184 dimethiconeand trisiloxane 13.63% 10.00% 40.00% Water N/A 46.00% 20.00% 60.00%Vitamin-C complex Ascorbic Acid 0.08% 0.05% 0.50% Jeecide CAP-5Phenoxyethanol, Caprylyl 0.33% 1.00% Glycol, Potassium Sorbate, Aqua,Hexylene Glycol Tween 20 Polysorbate 20 0.33% 5.00% Vitamin-A complexVitamin A Palmitate 1.7 MIU/g 0.40% 5.00% Vitamin-E complex Vitamin EAcetate 0.10% 5.00% Reactive constituent N/A 35.00% 30.00% 60.00% andReinforcing constituent composition (Vinyl, hydride, fumed silica) fromabove total 100.00%

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific polypeptides, nucleic acids, methods, assays and reagentsdescribed herein. Such equivalents are considered to be within the scopeof this invention and are covered by the following claims.

We claim:
 1. A therapeutic formulation for the formation of a film overthe skin of a subject, comprising: a) a reactive reinforcing componentcomprising (i) a reactive constituent comprising as ingredients at leastone vinyl functionalized organopolysiloxane and at least one hydridefunctionalized polysiloxane, wherein said reactive reinforcing componenthas a molar ratio of vinyl to hydride functional groups of about 1:10 toabout 1:100, and (ii) a reinforcing constituent; and b) a cross-linkingcomponent; wherein after said cross-linking component is contacted withthe reactive reinforcing component, a filmed is formed in situ on saidskin.
 2. The therapeutic formulation of claim 1, wherein said reactivereinforcing component has a viscosity of between about 50,000 and500,000 cSt or cP at 25° C.
 3. The therapeutic formulation of claim 1,wherein said vinyl functionalized organopolysiloxane is a combination ofat least one high viscosity organopolysiloxane and at least one lowviscosity organopolysiloxane.
 4. The therapeutic formulation of claim 3,wherein said high viscosity organopolysiloxane has a viscosity of about100,000 to about 500,000 cSt or cP at 25° C. and said low viscosityorganopolysiloxane has a viscosity of about 200 to about 50,000 cSt orcP at 25° C.
 5. The therapeutic formulation of claim 3, wherein saidhigh viscosity organopolysiloxane comprises vinyl terminatedorganopolysiloxane and said low viscosity organopolysiloxane comprisesvinyl terminated organopolysiloxane.
 6. The therapeutic formulation ofclaim 5, wherein said high viscosity organopolysiloxane comprises vinylterminated polydimethylsiloxane and said low viscosityorganopolysiloxane comprises vinyl terminated polydimethylsiloxane. 7.The therapeutic formulation of claim 3, wherein said low viscosityorganopolysiloxane has a viscosity of about 500 to about 50,000 cSt orcP at 25° C.
 8. The therapeutic formulation of claim 1, wherein saidhydride functionalized polysiloxane has a viscosity of about 5 to about11,000 cSt or cP at 25° C.
 9. The therapeutic formulation of claim 1,wherein said hydride functionalized polysiloxane is alkyl terminated.10. The therapeutic formulation of claim 1, wherein said hydridefunctionalized polysiloxane comprises trimethylsiloxy terminatedmethylhydrosiloxane-dimethylsiloxane copolymers.
 11. The therapeuticformulation of claim 1, wherein said hydride functionalized polysiloxanehas at least 2 Si-H units on average.
 12. The therapeutic formulation ofclaim 1, wherein said organopolysiloxanes are polymers of formula II andsaid hydride functionalized polysiloxane is a polymer of formula III:

wherein R^(1a′), R^(3a′), R^(4a′), R^(5a′), R^(6a′), R^(8a′), R^(9a′)and R^(10a′) are in each occurrence independently C₁₋₂₀ alkyl, C₂₋₂₀alkenyl, C₅₋₁₀ aryl, hydroxyl or C₁₋₂₀ alkoxyl; p and q are eachindependently an integer from between 10 and 6000; R^(1b), R^(2b),R^(3b), R^(6b), R^(7b) and R^(8b) are independently selected from C₁₋₂₀alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl and C₁₋₂₀ alkoxyl; R^(4b),R^(5b), R^(9b) and R^(10b) are in each occurrence independently selectedfrom hydrogen, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₅₋₁₀ aryl, hydroxyl andC₁₋₂₀ alkoxyl, wherein at least two of R^(4b), R^(5b), R^(9b) andR^(10b) are hydrogen; m and n are each independently an integer frombetween 10 and
 6000. 13. The formulation of claim 12, wherein R^(1b),R^(2b), R^(3b), R^(6b), R^(7b) and R^(8b) are C₁₋₂₀ alkyl.
 14. Thetherapeutic formulation of claim 1, wherein said reactive reinforcingcomponent has a vinyl to functional hydride molar ratio of about 1:10 toabout 1:50.
 15. The therapeutic formulation of claim 1, wherein saidreinforcing constituent is selected from the group consisting ofoptionally surface treated mica, zinc oxide, titanium dioxide, aluminumoxide, clay or silica.
 16. The therapeutic formulation of claim 15,wherein said reinforcing constituent has an average particle size ofbetween about 1 and about 20 μm.
 17. The therapeutic formulation ofclaim 1, wherein the crosslinking component comprises a metal catalyst.18. The therapeutic formulation of claim 17, wherein the concentrationof the catalyst in the cross-linking component is about 0.005 to about0.05% w/w.
 19. The composition of claim 1, wherein said film has anappearance of natural skin of said subject.
 20. The therapeuticformulation of claim 1, wherein the crosslinking component comprises oneor more ingredients selected from platinum carbonylcyclovinylmethylsiloxane complexes, platinumdivinyltetramethyldisiloxane complexes, platinumcyclovinylmethylsiloxane complexes, platinum octanaldehyde/octanolcomplexes, Tris (dibutylsulfide) Rhodium trichloride, tin II octoate,Tin II neodecanoate, dibutyltin diisooctylmaleate, Di-n-butylbis(2,4pentanedionate)tin, di-n-butylbutoxychlorotin, dibutyltin dilaurate,dimethyltin dineodecanoate, dimethylhydroxy(oleate)tin and tin IIoleate, or a combination thereof.
 21. The therapeutic formulation ofclaim 20, wherein the concentration of said one or more ingredients inthe cross-linking component is about 0.005 to about 0.05% w/w.
 22. Thetherapeutic formulation of claim 1, wherein said formulation is fortreating a wound.
 23. The therapeutic formulation of claim 1, whereinsaid formulation is for treating a headache.
 24. The therapeuticformulation of claim 1, wherein said formulation is for delivering anagent to said subject.
 25. The therapeutic formulation of claim 1,wherein said formulation is for delivering a therapeutic agent to saidsubject.
 26. A method for treating wounds, comprising applying to awound on a subject a formulation comprising: a) a reactive reinforcingcomponent comprising (i) a reactive constituent comprising asingredients at least one vinyl functionalized organopolysiloxane and atleast one hydride functionalized polysiloxane, wherein said reactivereinforcing component has a molar ratio of vinyl to hydride functionalgroups of about 1:10 to about 1:100, and (ii) a reinforcing constituent;and b) a cross-linking component; wherein after said cross-linkingcomponent is contacted with the reactive reinforcing component, a filmis formed in situ on said wound, thereby treating the wound.
 27. Themethod of claim 26, wherein the reactive reinforcing component has aviscosity of between about 50,000 and 500,000 cSt or cP at 25° C. 28.The method of claim 26, wherein the reactive reinforcing component has avinyl to functional hydride ratio of between about 1:10 and about 1:50.29. The method of claim 26, wherein said vinyl functionalizedorganopolysiloxane is a high viscosity organopolysiloxane or a lowviscosity organopolysiloxane or a combination thereof.
 30. The method ofclaim 26, wherein said reinforcing constituent is selected from thegroup consisting of optionally surface treated mica, zinc oxide,titanium dioxide, aluminum oxide, clay or silica.
 31. The method ofclaim 26, wherein the film is applied to the skin for at least 1 hour,at least 4 hours, at least 10 hours, at least 16 hours or at least 24hours.
 32. A method for delivering an agent to a subject, comprisingapplying to the subject's skin a formulation comprising: a) a reactivereinforcing component comprising (i) a reactive constituent comprisingas ingredients at least one vinyl functionalized organopolysiloxane andat least one hydride functionalized polysiloxane, wherein said reactivereinforcing component has a molar ratio of vinyl to hydride functionalgroups of about 1:10 to about 1:100, (ii) a reinforcing constituent, and(iii) optionally one or more agents; and b) a cross-linking componentoptionally comprising one or more agents; wherein after saidcross-linking component is contacted with the reactive reinforcingcomponent, a film is formed in situ on said skin, thereby delivering theagent to the subject; wherein the one or more agents is present in atleast a) or b).
 33. The method of claim 32, wherein the agent is acosmetic or a therapeutic agent.
 34. The method of claim 32, whereinsaid vinyl functionalized organopolysiloxane is a high viscosityorganopolysiloxane or a low viscosity organopolysiloxane or acombination thereof.
 35. The method of claim 32, wherein saidreinforcing constituent is selected from the group consisting ofoptionally surface treated mica, zinc oxide, titanium dioxide, aluminumoxide, clay or silica.
 36. A method of treating a stress headache in asubject comprising applying to an appropriate area of the subject's skina formulation in an amount effective to lift the subject's brow, theformulation comprising a) a reactive reinforcing component comprising(i) a reactive constituent comprising as ingredients at least one vinylfunctionalized organopolysiloxane and at least one hydridefunctionalized polysiloxane, wherein said reactive reinforcing componenthas a molar ratio of vinyl to hydride functional groups of about 1:10 toabout 1:100, and (ii) a reinforcing constituent; and b) a cross-linkingcomponent; wherein after said cross-linking component is contacted withthe reactive reinforcing component, a film is formed in situ on saidskin, thereby treating the stress headache by lifting the brow.
 37. Themethod of claim 36, wherein said vinyl functionalized organopolysiloxaneis a high viscosity organopolysiloxane or a low viscosityorganopolysiloxane or a combination thereof.
 38. The method of claim 36,wherein said reinforcing constituent is selected from the groupconsisting of optionally surface treated mica, zinc oxide, titaniumdioxide, aluminum oxide, clay or silica.